Herbicidal substituted sulphonylaminoazoles

ABSTRACT

Herbicidal substituted sulphonylaminoazoles of the formula ##STR1## in which R 1  is optionally substituted alkyl, aralkyl, aryl or heteroaryl, 
     R 2  is hydrogen or --SO 2  --R 1 , 
     R 3  is hydrogen, halogen, hydroxyl, mercapto, amino, or an optionally substituted alkyl, alkoxy, alkylthio, alkylamino or dialkylamino radical, 
     A is CH, nitrogen or, 
     at least one of A, D and E is ##STR2## and the others may be that or CH or nitrogen, and X, Y and Z each is nitrogen or optionally substituted C, and salts thereof.

This is a division of application Ser. No. 504,442, filed Apr. 3, 1990,now U.S. Pat. No. 5,012,082, which is a division of application Ser. No.317,219, filed 2/28/89, now U.S. Pat. No. 4,941,912.

The invention relates to novel substituted sulphonylaminoazoles,processes and new intermediates for their preparation and their use asherbicides.

It is known that 3-amino-1,2,4-triazole (amitrole) can be used as aherbicide (cf. Science 145 (1964), 97). However, the action of thiscompound is not satisfactory in all respects.

The new substituted sulphonylaminoazoles of the general formula (I)##STR3## in which R¹ stands for an optionally substituted radical fromthe series comprising alkyl, aralkyl, aryl and heteroaryl,

R² stands for hydrogen or the grouping --SO₂ --R¹, wherein

R¹ has the abovementioned meaning,

R³ stands for hydrogen, halogen, hydroxyl, mercapto, amino or anoptionally substituted radical from the series comprising alkyl, alkoxy,alkylthio, alkylamino and dialkylamino,

A stands for a CH grouping, for nitrogen or the grouping ##STR4## Dstands for nitrogen or the grouping ##STR5## E stands for nitrogen orthe grouping ##STR6## one of each of the radicals A, D or E in each casestanding for the grouping ##STR7## wherein R⁴ stands for hydrogen,halogen, hydroxyl, amino or an optionally substituted radical from theseries comprising alkyl, alkoxy, alkylthio, alkylamino and dialkylamino,

X stands for nitrogen or a CH grouping,

Y stands for nitrogen or a CR⁵ grouping wherein

R⁵ stands for hydrogen, halogen, cyano, alkyl, formyl, alkylcarbonyl oralkoxycarbonyl, and

Z stands for nitrogen or a CR⁶ grouping wherein

R⁶ stands for hydrogen, halogen, hydroxyl, amino or an optionallysubstituted radical from the series comprising alkyl, alkoxy, alkylthio,alkylamino and dialkylamino,

and salts of the compounds of the formula (I) have now been found.

The general formula (I) stands for the possible isomers of the formulae(IA), (IB) and (IC) ##STR8## in which R¹, R², R³, R⁴, X, Y and Z havethe abovementioned meanings and

A' stands for nitrogen or a CH grouping,

and for mixtures of these isomers.

The new substituted sulphonylaminoazoles of the general formula (I) areobtained in a process in which

(a) substituted aminoazoles of the general formula (II) ##STR9## inwhich A, D, E and R³ have the abovementioned meanings,

are reacted with sulphonyl halides or sulphonic anhydrides of thegeneral formula (III)

    R.sup.1 --SO.sub.2 --Q                                     (III)

in which

R¹ has the abovementioned meaning and

Q stands for fluorine, chlorine, bromine or the grouping --O--SO₂ --R¹,

wherein

R¹ has the abovementioned meaning,

if appropriate in the presence of an acid acceptor, if appropriate inthe presence of a catalyst and if appropriate in the presence of adiluent, and in which, if appropriate, the resulting compounds of theformula (I) in which

R² stands for the grouping --SO₂ --R¹,

are reacted with desulphonylating agents, if appropriate in the presenceof diluents, to give compounds of the formula (I) in which

R² stands for hydrogen,

or in which

(b) sulphonylated aminoguanidines of the general formulae (IVA) or (IVB)##STR10## in which R¹, R⁴, X, Y and Z have the abovementioned meanings

or tautomers of the compounds of the formulae (IVA) and (IVB) ormixtures of the compounds of the formulae (IVA) or (IVB) and thetautomers possible in each case are reacted with ester(amide)s of thegeneral formula (V) (i.e. orthoesters or amide acetals) ##STR11## inwhich R³ has the abovementioned meaning,

R stands for alkyl and

Q¹ stands for alkoxy or dialkylamino,

if appropriate in the presence of a diluent, or in which

(c) substituted aminopyrazolines of the general formula (VI) ##STR12##in which R⁴, X, Y and Z have the abovementioned meanings,

are reacted with sulphonyl halides or sulphonic anhydrides of thegeneral formula (III)

    R.sup.1 --SO.sub.2 --Q                                     (III)

in which

R¹ has the abovementioned meaning and

Q stands for fluorine, chlorine, bromine or the grouping --O--SO₂ --R¹

wherein R¹ has the abovementioned meaning, in the presence of(atmospheric) oxygen, if appropriate in the presence of an acid acceptorand if appropriate in the presence of a diluent, and if appropriate theresulting compounds of the formula (I), in which

R² stands for the grouping --SO₂ --R¹,

are reacted with desulphonylating agents, if appropriate in the presenceof diluents, to give compounds of the formula (I), in which

R² stands for hydrogen,

and if appropriate the products obtained by processes (a), (b) or (c)are converted to salts by customary methods.

Some of the compounds of the formula (I) according to the invention canalso be obtained as outlined below (R¹, R⁴, X, Y, Z as defined above; Q²for example SCH₃ or OC₆ H₅): ##STR13## The new substitutedsulphonylaminoazoles of the general formula (I) are distinguished by apowerful herbicidal activity. These compounds represent a chemicallynovel class of herbicides. Surprisingly, the new compounds of theformula (I) show a considerably better herbicidal action than the knownherbicide aminotrizole (amitrole) which has a similar structure.

The invention preferably relates to compounds of the formula (I) inwhich

R¹ stands for the radical ##STR14## wherein R⁷ and R⁸ are identical ordifferent and stand for hydrogen, fluorine, chlorine, bromine, iodine,cyano, nitro, C₁ -C₆ -alkyl [which is optionally substituted byfluorine, chlorine, bromine, cyano, carboxyl, C₁ -C₄ -alkoxycarbonyl, C₁-C₄ -alkylamino-carbonyl, di-(C₁ -C₄ -alkyl)-aminocarbonyl, hydroxyl, C₁-C₄ -alkoxy, formyloxy, C₁ -C₄ -alkyl-carbonyloxy, C₁ -C₄-alkoxycarbonyloxy, C₁ -C₄ -alkylamino-carbonyloxy, C₁ -C₄ -alkylthio,C₁ -C₄ -alkylsulphinyl, C₁ -C₄ -alkylsulphonyl, di-(C₁ -C₄-alkyl)-aminosulphonyl, C₃ -C₆ -cycloalkyl or phenyl], for C₂ -C₆-alkenyl [which is optionally substituted by fluorine, chlorine,bromine, cyano, C₁ -C₄ -alkoxy-carbonyl, carboxyl or phenyl], for C₂ -C₆-alkinyl [which is optionally substituted by fluorine, chlorine,bromine, cyano, C₁ -C₄ -alkoxycarbonyl, carboxyl or phenyl], for C₁ -C₄-alkoxy [which is optionally substituted by fluorine, chlorine, bromine,cyano, carboxyl, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkoxy, C₁ -C₄-alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl], for C₁-C₄ -alkylthio [which is optionally substituted by fluorine, chlorine,bromine, cyano, carboxyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄ -alkylthio, C₁-C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl], for C₃ -C₆ -alkenyloxy[which is optionally substituted by fluorine, chlorine, bromine, cyanoor C₁ -C₄ -cyano or C₁ -C₄ -alkoxycarbonyl], for C₂ -C₆ -alkenylthio[which is optionally substituted by fluorine, chlorine, bromine, cyano,nitro, C₁ -C₃ -alkylthio or C₁ -C₄ -alkoxycarbonyl], C₃ -C₆ -alkinyloxy,C₃ -C₆ -alkinylthio or for the radical --S(O)_(p) --R⁹, p standing forthe numbers 1 or 2 and

R⁹ standing for C₁ -C₄ -alkyl [which is optionally substituted byfluorine, chlorine, bromine, cyano or C₁ -C₄ -alkoxy-carbonyl], C₃ -C₆-alkenyl, C₃ -C₆ -alkinyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxy-C₁ -C₄-alkylamino, C₁ -C₄ -alkylamino, di-(C₁ -C₄ -alkyl)-amino or for theradical --NHOR¹⁰,

R¹⁰ standing for C₁ -C₆ -alkyl [which is optionally substituted byfluorine, chlorine, cyano, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-alkylsulphinyl, C₁ -C₄ -alkylsulphonyl, C₁ -C₄ -alkyl-carbonyl, C₁ -C₄-alkoxy-carbonyl, C₁ -C₄ -alkylamino-carbonyl or di-(C₁ -C₄-alkyl)-amino-carbonyl], for C₃ -C₆ -alkenyl [which is optionallysubstituted by fluorine, chlorine or bromine], C₃ -C₆ -alkinyl, C₃ -C₆-cycloalkyl, C₃ -C₆ -cycloalkyl-C₁ -C₂ -alkyl, phenyl-C₁ -C₂ -alkyl[which is optionally substituted by fluorine, chlorine, nitro, cyano, C₁-C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₄ -alkoxy-carbonyl], for benzhydrylor for phenyl [which is optionally substituted by fluorine, chlorine,nitro, cyano, C₁ -C₄ -alkyl, trifluoromethyl, C₁ -C₄ -alkoxy, C₁ -C₂-fluoroalkoxy, C₁ -C₄ -alkylthio, trifluoromethylthio or C₁ -C₄-alkoxy-carbonyl], R⁷ and R⁸ furthermore stand for phenyl or phenoxy,for C₁ -C₄ -alkylcarbonylamino, C₁ -C₄ -alkoxycarbonylamino, C₁ -C₄-alkylamino-carbonylamino, di-(C₁ -C₄ -alkyl)-amino-carbonylamino, orfor the radical --CO--R¹¹,

R¹¹ standing for C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, C₃ -C₆ -cycloalkoxy, C₃-C₆ -alkenyloxy, C₁ -C₄ -alkylthio, amino, C₁ -C₄ -alkylamino, C₁ -C₄-alkoxyamino, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl-amino or di-(C₁ -C₄-alkyl)-amino [which are optionally substituted by fluorine and/orchlorine], R⁷ and R⁸ furthermore stand for C₁ -C₄ -alkylsulphonyloxy,di-(C₁ -C₄ -alkyl)-aminosulphonylamino or for the radical --CH═N--R¹²,

R¹² standing for C₁ -C₆ -alkyl which is optionally substituted byfluorine, chlorine, cyano, carboxyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio,C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl, for benzyl which isoptionally substituted by fluorine or chlorine, for C₃ -C₆ -alkenyl orC₃ -C₆ -alkinyl, each of which is optionally substituted by fluorine orchlorine, for phenyl which is optionally substituted by fluorine,chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, trifluoromethyl,trifluoromethoxy or trifluoromethylthio, for C₁ -C₆ -alkoxy, C₃ -C₆-alkenoxy, C₃ -C₆ -alkinoxy or benzyloxy, each of which is optionallysubstituted by fluorine and/or chlorine, for amino, C₁ -C₄ -alkylamino,di-(C₁ -C₄ -alkyl)-amino, phenylamino, C₁ -C₄ -alkyl-carbonyl-amino, C₁-C₄ -alkoxy-carbonylamino, C₁ -C₄ -alkyl-sulphonylamino or forphenylsulphonylamino which is optionally substituted by fluorine,chlorine, bromine or methyl,

wherein furthermore

R¹ stands for the radical ##STR15## wherein R¹³ stands for hydrogen orC₁ -C₄ -alkyl,

R¹⁴ and R¹⁵ are identical or different and stand for hydrogen, fluorine,chlorine, bromine, nitro, cyano, C₁ -C₄ -alkyl [which is optionallysubstituted by fluorine and/or chlorine], C₁ -C₄ -alkoxy [which isoptionally substituted by fluorine and/or chlorine], carboxyl, C₁ -C₄-alkoxy-carbonyl, C₁ -C₄ -alkylsulphonyl or di-(C₁ -C₄-alkyl)aminosulphonyl;

wherein furthermore

R¹ stands for the radical ##STR16## wherein R¹⁶ and R¹⁷ are identical ordifferent and stand for hydrogen, fluorine, chlorine, bromine, nitro,cyano, C₁ -C₄ -alkyl [which is optionally substituted by fluorine and/orchlorine] or C₁ -C₄ -alkoxy [which is optionally substituted by fluorineand/or chlorine];

wherein furthermore

R¹ stands for the radical ##STR17## wherein R¹⁸ and R¹⁹ are identical ordifferent and stand for hydrogen, fluorine, chlorine, bromine, nitro,cyano, C₁ -C₄ -alkyl [which is optionally substituted by fluorine and/orchlorine], C₂ -C₄ -alkenyl [which is optionally substituted by fluorineand/or chlorine], C₁ -C₄ -alkoxy [which is optionally substituted byfluorine and/or chlorine], for C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinylor C₁ -C₄ -alkylsulphonyl [which are optionally substituted by fluorineand/or chlorine], and for di-(C₁ -C₄ -alkyl)aminosulphonyl, C₁ -C₄-alkoxy-carbonyl, dimethylaminocarbonyl or dioxolanyl;

wherein furthermore

R¹ stands for the radical ##STR18## wherein R²⁰ and R²¹ are identical ordifferent and stand for hydrogen, fluorine, chlorine, bromine, C₁ -C₄-alkyl [which is optionally substituted by fluorine and/or bromine], C₁-C₄ -alkoxy [which is optionally substituted by fluorine and/orchlorine], for C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄-alkylsulphonyl [which are optionally substituted by fluorine and/orchlorine], or for di-(C₁ -C₄ -alkyl)-aminosulphonyl;

wherein furthermore

R¹ stands for the radical ##STR19## wherein R²² and R²³ are identical ordifferent and stand for hydrogen, fluorine, chlorine, bromine, cyano,nitro, C₁ -C₄ -alkyl [which is optionally substituted by fluorine,chlorine, C₁ -C₄ -alkoxy and/or C₁ -C₄ -halogenoalkoxy], C₁ -C₄ -alkoxy[which is optionally substituted by fluorine and/or chlorine], C₁ -C₄-alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl [which isoptionally substituted by fluorine and/or chlorine], di-(C₁ -C₄-alkyl)-amino-sulphonyl or C₁ -C₄ -alkoxycarbonyl, and

A¹ stands for oxygen, sulphur or the grouping N--Z¹,

Z¹ standing for hydrogen, C₁ -C₄ -alkyl [which is optionally substitutedby fluorine, chlorine, bromine or cyano], C₃ -C₆ -cycloalkyl, benzyl,phenyl [which is optionally substituted by fluorine, chlorine, bromineor nitro], C₁ -C₄ -alkylcarbonyl, C₁ -C₄ -alkoxy-carbonyl or di-(C₁ -C₄-alkyl)-aminocarbonyl;

wherein furthermore

R¹ stands for the radical ##STR20## wherein R²⁴ and R²⁵ are identical ordifferent and stand for hydrogen, C₁ -C₄ -alkyl, halogen, C₁ -C₄-alkoxycarbonyl, C₁ -C₄ -alkoxy or C₁ -C₄ -halogenoalkoxy,

Y¹ stands for sulphur or the grouping N--R²⁶,

R²⁶ standing for hydrogen or C₁ -C₄ -alkyl;

wherein furthermore

R¹ stands for the radical ##STR21## wherein R²⁷ stands for hydrogen, C₁-C₄ -alkyl, phenyl or (iso)quinolinyl,

R²⁸ stands for hydrogen, halogen, cyano, nitro, C₁ -C₄ -alkyl [which isoptionally substituted by fluorine and/or chlorine], C₁ -C₄ -alkoxy[which is optionally substituted by fluorine and/or chlorine],dioxolanyl or C₁ -C₄ -alkoxy-carbonyl and R²⁹ stands for hydrogen,halogen or C₁ -C₄ -alkyl;

wherein furthermore

R¹ stands for the radical ##STR22## wherein R³⁰ stands for hydrogen,halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy-carbonyl;

wherein furthermore

R¹ stands for the radical ##STR23## wherein R³¹ stands for C₁ -C₄ -alkyland

R³² stands for C₁ -C₄ -alkyl,

wherein furthermore

R₁ stands for the radical ##STR24## wherein R³³ stands for hydrogen ormethyl;

in which furthermore

R² stands for hydrogen or for the grouping --SO₂ --R¹,

wherein

R¹ has the preferred meaning given above;

in which furthermore

R³ stands for hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl,mercapto, amino or for a radical from the series comprising C₁ -C₄-alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylamino and di-(C₁-C₄ -alkyl)amino, which radical is optionally substituted by fluorineand/or chlorine,

A stands for nitrogen, a CH grouping or the grouping ##STR25## D standsfor nitrogen or the grouping ##STR26## E stands for nitrogen or thegrouping ##STR27## one of each of the radicals A, D or E in each casestanding for the grouping ##STR28## wherein R⁴ stands for hydrogen,fluorine, chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -halogenoalkyl, C₁-C₂ -alkoxy-C₁ -C₂ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -halogenoalkoxy, C₁-C₄ -alkylthio, C₁ -C₄ -halogenoalkylthio, amino, C₁ -C₄ -alkyl-amino,dimethylamino or diethylamino,

X stands for nitrogen or a CH grouping,

Y stands for nitrogen or a CR⁵ grouping,

wherein

R⁵ stands for hydrogen, fluorine, chlorine, bromine, cyano, methyl,formyl, acetyl, methoxycarbonyl or ethoxycarbonyl and

Z stands for nitrogen or a CR⁶ grouping

wherein

R⁶ stands for hydrogen, fluorine, chlorine, bromine, C₁ -C₄ -alkyl, C₁-C₄ -halogenoalkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -halogenoalkoxy, C₁ -C₄-alkylthio, C₁ -C₄ -alkyl-amino, dimethylamino or diethylamino.

In particular, the invention relates to compounds of the formula (I) inwhich

R¹ stands for the radial ##STR29## wherein R⁷ stands for flourine,chlorine, bromine, methyl, trifluoromethyl, methoxy, difluoromethoxy,trifluoromethoxy, C₁ -C₃ -alkylthio, C₁ -C₃ -alkylsulphinyl, C₁ -C₃-alkylsulphonyl, dimethylaminosulphonyl,N-methoxy-N-methylaminosulphonyl, phenyl, phenoxy or C₁ -C₃-alkoxy-carbonyl and

R⁸ stands for hydrogen, fluorine or chlorine;

wherein furthermore

R¹ stands for the radical ##STR30## wherein R¹³ stands for hydrogen,

R¹⁴ stands for fluorine, chlorine, bromine, methyl, methoxy,difluoromethoxy, trifluoromethoxy, ethoxy, methoxycarbonyl,ethoxycarbonyl, methylsulphonyl or dimethylaminosulphonyl and

R¹⁵ stands for hydrogen, fluorine or chlorine;

wherein furthermore

R¹ stands for the radical ##STR31## wherein R stands for C₁ -C₄ -alkyl,or

R¹ stands for the radical ##STR32## wherein R stands for C₁ -C₄ -alkyl,or

R¹ stands for the radical ##STR33## wherein R³⁰ stands for hydrogen,chlorine, methyl, ethyl, methoxycarbonyl or ethoxycarbonyl; in whichfurthermore

R² stands for hydrogen or for the grouping --SO₂ --R¹,

wherein

R¹ has the meaning given above as particularly preferred,

R³ stands for hydrogen, methyl, methoxy or methylthio,

A stands for nitrogen, a CH grouping or the grouping ##STR34## D standsfor nitrogen or the grouping ##STR35## E stands for nitrogen or thegrouping ##STR36## one of each of the radicals A, D or E in each casestanding for the grouping ##STR37## wherein R⁴ stands for hydrogen,fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, ethoxy,difluoromethoxy, methylthio, ethylthio, amino, methylamino, ethylamino,dimethylamino or diethylamino,

X stands for nitrogen or a CH grouping,

Y stands for nitrogen or a CR⁵ grouping,

wherein

R⁵ stands for hydrogen, fluorine, chlorine or methyl, and

Z stands for nitrogen or a CR⁶ grouping

wherein

R⁶ stands for hydrogen, fluorine, chlorine, bromine, methyl, ethyl,trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, difluoromethoxy,methylthio, ethylthio, methylamino, ethylamino, dimethylamino ordiethylamino.

Very particularly preferred compounds of the formula (IA)--above--arethose in which R¹, R², R³, R⁴, X, Y and Z have those meanings which havebeen mentioned in connection with the description of the compounds ofthe formula (I) according to the invention as being particularlypreferred for R¹, R², R³, R⁴, X, Y and Z. A' particularly preferablystands for nitrogen or a CH grouping.

Furthermore particularly preferred compounds of the general formula(IB)--above--in which R¹, R², R³, R⁴, X, Y and Z have those meaningswhich have been mentioned in connection with the description of thecompounds of the formula (I) according to the invention as beingparticularly preferred for R¹, R², R³, R⁴, X, Y and Z. A' particularlypreferably stands for nitrogen or a CH grouping.

Moreover, particularly preferred compounds of the general formula(IC)--above--are those in which R¹, R², R³, R⁴, X, Y and Z have thosemeanings which have been mentioned in connection with the description ofthe compounds of the formula (I) according to the invention as beingparticularly preferred for R¹, R², R³, R⁴, X, Y and Z.

The invention furthermore relates to salts of compounds of the formula(I) formed with

α) protonic acids, such as, for example, hydrochloric acid, sulphuricacid, phosphoric acid, methanesulphonic acid, benzene- orp-toluenesulphonic acid, or naphthalenemono- or di-sulphonic acids, or

β) bases, such as, for example, the hydroxides, hydrides, amides orcarbonates of sodium, potassium or calcium, sodium C₁ -C₄ -alkanoxides,potassium C₁ -C₄ -alkanoxides, ammonia, C₁ -C₄ -alkylamines, di-(C₁ -C₄-alkyl)-amines or tri-(C₁ -C₄ -alkyl)-amines.

If, for example,5-amino-3-methyl-1-(4,6-dimethoxy-1,3,5-triazin-2-yl)-1,2,4-triazole and2-fluorobenzenesulphonyl chloride (2 mole equivalents) are used asstarting substances, the course of the reaction in the process (a)according to the invention can be outlined by the following equation:##STR38##

If, for example,N'-(4,6-dimethoxy-pyrimidin-2-yl-amino)-N"-(2-methoxycarbonyl-benzylsulphonyl)-guanidineand trimethyl orthoformate are used as starting substances, the courseof the reaction in process (b) according to the invention can beoutlined by the following equation: ##STR39##

If, for example, 3-amino-1-(4,6-dimethylpyrimidin-2-yl)-2-pyrazoline and2-methylsulphonylbenzenesulphonyl chloride are used as startingsubstances, and if the reaction is carried out under an (atmospheric)oxygen atmosphere, the course of the reaction in process (c) accordingto the invention can be outlined by the following equation: ##STR40##

Formula (II) provides a general definition of the substitutedaminoazoles to be used as starting substances in process (a) accordingto the invention for the preparation of compounds of the formula (I).

In formula (II), A, D, E and R³ preferably, or in particular, have thosemeanings which have already been preferentially mentioned above, ormentioned above as particularly preferred, for A, D, E and R³ inconnection with the description of the compounds of the formula (I)according to the invention.

The general formula (II) stands for the possible isomers of the formulae(IIA), (IIB) and (IIC) ##STR41## and for mixtures of these isomers.

In formulae (IIA), (IIB) and (IIC), A', R³, R⁴, X, Y and Z preferably,or in particular, have those meanings which have already beenpreferentially mentioned above, or mentioned as particularly preferred,for A', R³, R⁴, X, Y and Z in connection with the description of thecompounds of the formula (I) according to the invention.

Examples of the starting substances of the formulae (IIA), (IIB) and(IIC)--and thus also for the compounds of the formula (II)--are listedin Table 1 below. Thus, the meanings of the variables A, R³, R⁴, X, Yand Z, each of which is indicated line by line for individual examples,in each individual case stand for the isomers of the formulae (IIA),(IIB) and for the isomers of the formula (IIC).

                  TABLE 1                                                         ______________________________________                                        Examples of the starting substances of the                                    formulae (IIA), (IIB) and (IIC)                                               ______________________________________                                         ##STR42##                   (IIA)                                             ##STR43##                   (IIB)                                             ##STR44##                   (IIC)                                            A or A' R.sup.3  R.sup.4   X    Y     Z                                       ______________________________________                                        N       H        CH.sub.3  N    CH    CCH.sub.3                               N       H        CH.sub.3  N    CH    COCH.sub.3                              N       H        CH.sub.3  N    CH    COC.sub.2 H.sub.5                       N       H        OCH.sub.3 N    CH    COCH.sub.3                              N       H        OCH.sub.3 N    CH    CCl                                     N       H        H         N    CH    CCH.sub.3                               N       H        CF.sub.3  N    CH    COCH.sub.3                              N       H        OCH.sub.3 N    CH    COCHF.sub.2                             N       H        CH.sub.3  N    CH    COCHF.sub.2                             N       H        OCHF.sub.2                                                                              N    CH    COCHF.sub.2                             N       H        CH.sub.3  N    N     CCH.sub.3                               N       H        CH.sub.3  N    N     COCH.sub.3                              N       H        OCH.sub.3 N    N     COCH.sub.3                              N       H        OCH.sub.3 N    N     CCl                                     N       H        C.sub.2 H.sub.5                                                                         N    CH    COCH.sub.3                              N       H        C.sub.2 H.sub.5                                                                         N    N     COCH.sub.3                              N       CH.sub.3 CH.sub.3  N    CH    CCH.sub.3                               N       CH.sub.3 CH.sub.3  N    CH    COCH.sub.3                              N       CH.sub.3 OCH.sub.3 N    CH    COCH.sub.3                              N       CH.sub.3 OCH.sub.3 N    CH    CCl                                     N       CH.sub.3 H         N    CH    CCH.sub.3                               N       CH.sub.3 CF.sub.3  N    CH    COCH.sub.3                              N       CH.sub.3 OCH.sub.3 N    CH    COCHF.sub.2                             N       CH.sub.3 CH.sub.3  N    CH    COCHF.sub.2                             N       CH.sub.3 CH.sub.3  N    N     CCH.sub.3                               N       CH.sub.3 CH.sub.3  N    N     COCH.sub.3                              N       CH.sub.3 OCH.sub.3 N    N     COCH.sub.3                              N       CH.sub.3 C.sub.2 H.sub.5                                                                         N    CH    COCH.sub.3                              N       CH.sub.3 CH.sub.3  N    N     COC.sub.2 H.sub.5                       N       CH.sub.3 C.sub.2 H.sub.5                                                                         N    N     COCH.sub.3                              N       CH.sub.3 CH.sub.3  N    N     CCl                                     N       CH.sub.3 CH.sub.3  CH   N     CCH.sub.3                               N       CH.sub.3 OCH.sub.3 CH   N     COCH.sub.3                              N       CH.sub.3 CH.sub.3  N    CH    CSCH.sub.3                              N       H        CH.sub.3  N    CH    CN(CH.sub.3).sub.2                      N       H        OCH.sub.3 N    CH    CSCH.sub.3                              N       H        OCH.sub.3 N    N     CNHC.sub.2 H.sub.5                      N       H        OC.sub.2 H.sub.5                                                                        N    N     CNHCH.sub.3                             N       H        CH.sub.3  CH   CH    CCH.sub.3                               N       OCH.sub.3                                                                              CH.sub.3  N    CH    CCH.sub.3                               N       OCH.sub.3                                                                              CH.sub.3  N    CH    COCH.sub.3                              N       OCH.sub.3                                                                              OCH.sub.3 N    CH    COCH.sub.3                              N       OCH.sub.3                                                                              OCH.sub.3 N    CH    CCl                                     N       OCH.sub.3                                                                              H         N    CH    CCH.sub.3                               N       OCH.sub.3                                                                              CF.sub.3  N    CH    COCH.sub.3                              N       OCHF.sub.2                                                                             OCH.sub.3 N    CH    COCHF.sub.2                             N       OCH.sub.3                                                                              CH.sub.3  N    CH    COCHF.sub.2                             N       OCH.sub.3                                                                              CH.sub.3  N    N     CCH.sub.3                               N       OCH.sub.3                                                                              CH.sub.3  N    N     COCH.sub.3                              N       OCH.sub.3                                                                              OCH.sub.3 N    N     COCH.sub.3                              N       OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                         N    CH    COCH.sub.3                              N       OCH.sub.3                                                                              C.sub.2 H.sub.5                                                                         N    N     COCH.sub.3                              N       SCH.sub.3                                                                              CH.sub.3  N    CH    CCH.sub.3                               N       OCH.sub.3                                                                              CH.sub.3  N    N     COC.sub.2 H.sub.5                       N       SCH.sub.3                                                                              CH.sub.3  N    CH    COCH.sub.3                              N       SCH.sub.3                                                                              CH.sub.3  N    CH    COC.sub.2 H.sub.5                       N       SCH.sub.3                                                                              OCH.sub.3 N    CH    COCH.sub.3                              N       SCH.sub.3                                                                              OCH.sub.3 N    CH    CCl                                     N       SCH.sub.3                                                                              H         N    CH    CCH.sub.3                               N       SCH.sub.3                                                                              CF.sub.3  N    CH    COCH.sub.3                              N       SCH.sub.3                                                                              OCH.sub.3 N    CH    COCHF.sub.2                             N       SCH.sub.3                                                                              CH.sub.3  N    CH    COCHF.sub.2                             N       SCH.sub.3                                                                              OCHF.sub.2                                                                              N    CH    COCHF.sub.2                             N       SCH.sub.3                                                                              CH.sub.3  N    N     CCH.sub.3                               N       SCH.sub.3                                                                              CH.sub.3  N    N     COCH.sub.3                              N       SCH.sub.3                                                                              OCH.sub.3 N    N     COCH.sub.3                              N       SCH.sub.3                                                                              OCH.sub.3 N    N     CCl                                     N       SCH.sub.3                                                                              C.sub.2 H.sub.5                                                                         N    CH    COCH.sub.3                              N       SCH.sub.3                                                                              C.sub.2 H.sub.5                                                                         N    N     COCH.sub.3                              CH      H        CH.sub.3  N    CH    CCH.sub.3                               CH      H        CH.sub.3  N    CH    COCH.sub.3                              CH      H        OCH.sub.3 N    CH    COCH.sub.3                              CH      H        OCH.sub.3 N    CH    CCl                                     CH      H        CF.sub.3  N    CH    COCH.sub.3                              CH      H        OCH.sub.3 N    CH    COCHF.sub.2                             CH      H        CH.sub.3  N    CH    COCHF.sub.2                             CH      H        OCHF.sub.2                                                                              N    CH    COCHF.sub.2                             CH      H        CH.sub.3  N    N     CCH.sub.3                               CH      H        CH.sub.3  N    N     COCH.sub.3                              CH      H        OCH.sub.3 N    N     CCl                                     CH      H        C.sub.2 H.sub.5                                                                         N    CH    COCH.sub.3                              CH      H        C.sub.2 H.sub.5                                                                         N    N     COCH.sub.3                              ______________________________________                                    

Most of the starting substances of the formula (II)--and also those ofthe formulae (IIA), (IIB) and (IIC)--were hitherto not known from theliterature. New compounds of the formula (II) and of the formulae (IIA),(IIB) and (IIC) are, in particular, those in which A, or A', stands fornitrogen.

The compounds of the formula (II) are generally obtained as variouslycomposed mixtures of compounds of the formulae (IIA), (IIB) and (IIC) ina process in which

α) aminoazoles of the general formula (VII) ##STR45## in which A' and R³have the abovementioned meanings,

are reacted with azines of the general formula (VIII) ##STR46## in whichR⁴, X, Y and Z have the abovementioned meanings and

Q³ stands for halogen or alkylsulphonyl,

if appropriate in the presence of an acid acceptor, such as, forexample, potassium carbonate, and if appropriate in the presence of adiluent, such as, for example, acetonitrile or dimethylformamide, attemperatures from 0° C. to 150° C. or in which

β) hydrazinoazines of the general formula (IX) ##STR47## in which R⁴, X,Y and Z have the abovementioned meanings,

are reacted with S,S-dimethyl cyaniminodithiocarbonate of the formula(X) ##STR48## if appropriate in the presence of a diluent, such as, forexample, methanol or ethanol, at temperatures from 0° C. to 100° C., orin which

γ) aminoguanidines of the general formula (XIA) or (XIB) ##STR49## inwhich R⁴, X, Y and Z have the abovementioned meanings, or acid saltsthereof, such as, for example, the hydrochlorides,

are reacted with ester(amide)s of the general formula (V) ##STR50## inwhich R³, R and Q¹ have the abovementioned meanings,

if appropriate in the presence of a diluent, such as, for example,acetonitrile or dimethylformamide, at temperatures from 0° C. to 150° C.

Formula (VII) provides a general definition of the aminoazoles requiredas intermediates for this reaction. In formula (VII), A' and R³preferably, or in particular, have those meanings which have alreadybeen preferentially mentioned above, or mentioned as particularlypreferred, for A' and R³ in connection with the description of thecompounds of the formula (I) according to the invention.

Examples of the compounds of the formula (VII) which may be mentionedare: 3-amino-1,2,4-triazole, 3-amino-5-methyl-1,2,4-triazole,3-amino-5-methoxy-1,2,4-triazole, 3-amino-5-methylthio-1,2,4-triazole,3-aminopyrazole, 3-amino-5-methyl-pyrazole, 3-amino-5-methoxypyrazoleand 3-amino-5-methylthio-pyrazole.

The aminoazoles of the formula (VII) are known and/or can be prepared byprocesses known per se (cf. J. Org. Chem. 28 (1963), 1816-1821; loc.cit. 39 (1974), 1522-1526).

Formula (VIII) provides a general definition of the azines also requiredas intermediates. In formula (VIII), R⁴, X, Y and Z preferably, or inparticular, have those meanings which have already been preferentiallymentioned above, or mentioned above as particularly preferred, for R⁴,X, Y and Z in connection with the description of the compounds of theformula (I) according to the invention, and Q¹ preferably stands forfluorine, chlorine, bromine or C₁ -C₄ -alkylsulphonyl, in particular forchlorine or methylsulphonyl.

Examples of the compounds of the formula (VIII) which may be mentionedare: 2-chloro- and 2-methylsulphonyl-4,6-dimethyl-pyrimidine,-4-methyl-6-methoxy-pyrimidine, -4,6-dimethoxy-pyrimidine,-4-methyl-6-ethoxy-pyrimidine, -4-chloro-6-methoxy-pyrimidine,-4-methyl-pyrimidine, -4-chloro-6-methyl-pyrimidine,-4-trifluoromethyl-6-methoxy-pyrimidine,-4-methoxy-6-difluoromethoxy-pyrimidine,-4-methyl-6-difluoromethoxy-pyrimidine,-4,6-bis-difluoromethoxy-pyrimidine, -4-chloro-6-ethoxy-pyrimidine,-4,6-diethoxy-pyrimidine, -4,5-dichloro-6-methyl-pyrimidine,-4-methyl-5-chloro-6-methoxy-pyrimidine, -4,6-dichloro-pyrimidine,-4-ethyl-6-methoxy-pyrimidine, -5-chloro-4,6-dimethoxy-pyrimidine and-4,6-bis-trifluoromethyl-pyrimidine, furthermore2-chloro-4,6-dimethyl-s-triazine 2-chloro-4-methyl-6-methoxy-s-triazine,2-chloro-4,6-dimethoxy-s-triazine, 2,4-dichloro-6-methoxy-s-triazine,2-chloro-4-ethyl-6-methoxy-s-triazine and2-chloro-4-methyl-6-ethoxy-s-triazine.

The azines of the formula (VIII) are known and/or can be prepared byprocesses known per se (cf. J. Chem. Soc. 1957, 1830, 1833; J. Org.Chem. 26 (1961), 792; U.S. Pat. No. 3,308,119 and U.S. Pat. No.4,711,959).

Formula (IX) provides a general definition of the hydrazinoazines alsorequired as intermediates. In formula (IX), R⁴, X, Y and Z preferably,or in particular, have those meanings which have already beenpreferentially mentioned above, or mentioned above as particularlypreferred, for R⁴, X, Y and Z in connection with the description of thecompounds of the formula (I) according to the invention.

Examples of the compounds of the formula (IX) which may be mentionedare: 2-hydrazino-4,6-dimethyl-pyrimidine, 4-methyl-6-methoxypyrimidine,-4,6-dimethoxy-pyrimidine, -4-methyl-6-ethoxypyrimidine,-4-chloro-6-methoxy-pyrimidine, -4-methylpyrimidine,-4-chloro-6-methyl-pyrimidine, -4-trifluoromethyl-6-methoxy-pyrimidine,-4-methoxy-6-difluoromethoxypyrimidine,-4-methyl-6-difluoromethoxy-pyrimidine,-4,6-bis-difluoromethoxy-pyrimidine, -4-chloro-6-ethoxypyrimidine,-4,6-diethoxy-pyrimidine, -4,5-dichloro-6-methyl-pyrimidine,-4-methyl-5-chloro-6-methoxy-pyrimidine, -4,6-dichloro-pyrimidine,-4-ethyl-6-methoxy-pyrimidine, -5-chloro-4,6-dimethoxy-pyrimidine andalso -4,6-bis-trifluoromethyl-pyrimidine, furthermore2-hydrazino-4,6-dimethyl-s-triazine, -4-methyl-6-methoxy-s-triazine,-4,6-dimethoxy-s-triazine, -4-ethyl-6-methoxy-s-triazine and-4-methyl-6-ethoxy-s-triazine.

The hydrazinoazines of the formula (IX) are known and/or can be preparedby processes known per se (cf. Chem. Pharm. Bull. 11 (1963), 1382-1388).

In general, the compounds of the formula (IX) are obtained when azinesof the formula (VIII)--above--are reacted with hydrazine or hydrazinehydrate, if appropriate in the presence of a diluent, such as, forexample, ethanol, acetone, acetonitrile or dimethylformamide, and ifappropriate in the presence of a base, such as, for example, potassiumcarbonate or triethylamine, at temperatures from 0° C. to 100° C.

S,S-Dimethyl cyaniminodithiocarbonate, of the formula (X), which is alsorequired as an intermediate, is already known (cf. J. Org. Chem. 32(1967), 1566-1572).

Formulae (XIA) and (XIB) provide general definitions of theaminoguanidines also required as intermediates. In formulae (XIA) and(XIB), R⁴, X, Y and Z preferably, or in particular, have the meaningswhich have already been preferentially mentioned above, or mentionedabove as particularly preferred, for R⁴, X, Y and Z in connection withthe description of the compounds of the formula (I) according to theinvention.

Examples of the compounds of the formulae (XIA) and (XIB) are listed inTable 2 below. The meanings of the variables R⁴, X, Y and Z, each ofwhich is indicated line by line for individual examples, in eachindividual case stand for the isomers of the formula (XIA) and theformula (XIB)

                  TABLE 2                                                         ______________________________________                                        Examples of the compounds of the formulae (XIA) and (XIB)                     R.sup.4      X        Y         Z                                             ______________________________________                                        CH.sub.3     H        CH        C--CH.sub.3                                   CH.sub.3     N        CH        C--OCH.sub.3                                  CH.sub.3     N        CH        C--OC.sub.2 H.sub.5                           OCH.sub.3    N        CH        C--OCH.sub.3                                  OCH.sub.3    N        CH        C--Cl                                         H            N        CH        C--CH.sub.3                                   CF.sub.3     N        CH        C--OCH.sub.3                                  OCH.sub.3    N        CH        C--OCHF.sub.2                                 CH.sub.3     N        CH        C--OCHF.sub.2                                 OCHF.sub.2   N        CH        C--OCHF.sub.2                                 CH.sub.3     N        N         C--CH.sub.3                                   CH.sub.3     N        N         C--OCH.sub.3                                  OCH.sub.3    N        N         C--OCH.sub.3                                  C.sub.2 H.sub.5                                                                            N        CH        C--OCH.sub.3                                  C.sub.2 H.sub.5                                                                            N        N         C--OCH.sub.3                                  ______________________________________                                    

The aminoguanidines of the formulae (XIA) and (XIB) were hithertounknown from the literature.

In general, the new compounds of the formulae (XIA) and (XIB) areobtained when azines of the formula (VIII)--above--are reacted withaminoguanidine or an acid salt thereof, such as, for example, thehydrochloride or the hydrogen carbonate, if appropriate in the presenceof a diluent, such as, for example, ethanol, acetone, acetonitrile ordimethylformamide, and if appropriate in the presence of a base, suchas, for example, potassium carbonate or triethylamine, at temperaturesfrom 0° C. to 100° C.

The aminoguanidines of the formula (XIA) can also be obtained from knownS-methyl-isothioureidoazines of the formula (XII) ##STR51## in which R⁴,X, Y and Z have the abovementioned meanings,

and hydrazine or hydrazine hydrate, if appropriate in the presence of adiluent, such as, for example, ethanol or dioxane, at temperatures from0° C. to 100° C. (cf. EP-A 117,014/U.S. Pat. No. 4,689,070).

The aminoguanidines of the formula (XIB) can also be obtained byreacting hydrazinoazines of the formula (IX)--above--with cyanamide, ifappropriate in the presence of an acid, such as, for example,hydrochloric acid, and if appropriate in the presence of a diluent, suchas, for example, ethanol and/or water, at temperatures from 0° C. to100° C.

Formula (V) provides a general definition of the ester(amide)s alsorequired as intermediates. In formula (V), R³ preferably, or inparticular, has the meaning which has already been preferably mentionedabove, or mentioned above as particularly preferred, for R³ inconnection with the description of the compounds of the formula (I)according to the invention, R preferably stands for C₁ -C₄ -alkyl, inparticular for methyl or ethyl, and Q¹ preferably stands for C₁ -C₄-alkoxy or di-(C₁ -C₂)-alkylamino, in particular for methoxy, ethoxy ordimethylamino.

Examples of the compounds of the formula (V) which may be mentioned are:N,N-dimethylformamide dimethyl acetal and -diethyl acetal, trimethylorthoformate and triethyl orthoformate, trimethyl orthoacetate andtriethyl orthoacetate.

The compounds of the formula (V) are known chemicals for synthesis.

Formula (III) provides a general definition of the sulphonyl halides andsulphonic anhydrides also to be used as starting substances in theprocess according to the invention for the preparation of the newcompounds of the formula (I). In formula (III), R¹ preferably, or inparticular, has the meaning which has been preferentially mentionedabove, or mentioned above as particularly preferred, in context with thedescription of the compounds of the formula (I) according to theinvention, and Q preferably stands for chlorine.

Examples of the starting substances of the formula (III) which may bementioned are: benzenesulphonyl chloride, 2-chloro-, 3-chloro-,4-chloro-, 2,5-dichloro-, 2-fluoro-, 4-fluoro-, 2-bromo-, 4-bromo-,2-cyano-, 2-nitro-, 4-nitro-, 2-methyl-, 4-methyl-, 2-chloromethyl-,2-trifluoromethyl-, 2-methoxy-, 4-methoxy-, 2-methylthio-,2-trifluoromethylthio-, 2-difluoromethylthio-,2-cyclopropyloxycarbonyl-, 2-phenoxy-, 2-difluoromethoxy-,2-trifluoromethoxy-, 2-(2-chloroethoxy)-, 2-methylthiomethyl-,2-dimethylaminosulphonyl-, 2-phenyl-, 2-methoxycarbonyl-,2-ethoxycarbonyl-, 2-dimethylaminocarbonyl-and2-diethylaminocarbonylbenzenesulphonyl chloride and (2-chloro-phenyl)-,(2-cyano-phenyl)-, (2-methoxycarbonyl-phenyl)- and(2-trifluoromethoxy-phenyl)-methanesulphonyl chloride,2-chloro-6-methyl-benzenesulphonyl chloride and2,6-dichloro-benzenesulphonyl chloride.

The sulphonyl halides or sulphonic anhydrides of the formula (III) areknown and/or can be prepared by processes known per se (cf. J. Org.Chem. 33 (1968), 2104; J. Org. Chem. 25 (1960), 1824; DE-AS (GermanPublished Specification) 2,308,262; EP-OS (European PublishedSpecifications) 23,140, 23,141, 23,422, 35,893, 48,143, 51,466, 64,322,70,041, 44,808 and 44,809; U.S. Pat. Nos. 2,929,820, 4,282,242;4,348,220 and 4,372,778 and Angew. Chem. 93 (1981), 151).

The process (a) according to the invention for the preparation of thenew compounds of the formula (I) is preferably carried out usingdiluents. Suitable diluents in this process are virtually all inertorganic solvents. These preferably include aliphatic and aromatic,optionally halogenated hydrocarbons, such as pentane, hexane, heptane,cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene,xylene, methylene chloride, ethylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, ethers, such asdiethyl ether and dibutyl ether, glycol dimethyl ether, diglycoldimethyl ether, tetrahydrofuran and dioxane, ketones, such as acetone,methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone,esters, such as methyl acetate and ethyl acetate, nitriles, such as, forexample, acetonitrile and propionitrile, amides, such as, for example,dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, and alsodimethyl sulphoxide, tetramethylene sulphone, hexamethylphosphorictriamide and pyridine.

Acid acceptors which can be employed in the process (a) according to theinvention include all the acidbinding agents which can customarily beused for reactions of this type. Alkali metal hydroxides, such as, forexample, sodium hydroxide and potassium hydroxide, alkaline earth metalhydroxides, such as, for example, calcium hydroxide, alkali metalcarbonates and alkali metal alkoxides, such as sodium carbonate andpotassium carbonate, sodium tert.-butoxide and potassium tert.-butoxide,furthermore aliphatic, aromatic or heterocyclic amines, for exampletriethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine,pyridine, picoline, 1,5-diazabicyclo-[4,3,0]-non-5-ene (DBN),1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU) and1,4-diazabicyclo[2,2,2]-octane (DABCO) are preferably suitable.

Catalysts which can be used in the process according to the inventionare metal halides, such as, for example, aluminum chloride or zincchloride.

When carrying out process (a) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures from -50° C. to +50° C.,preferably at temperatures from -40° C. to +40° C.

For carrying out process (a) according to the invention, 1 to 5 moles,preferably 1 to 4 moles, of sulphonyl halide or sulphonic anhydride ofthe formula (III) are generally employed per mole of aminoazole of theformula (II). If disulphonylated compounds of the formula (I,R² =--SO₂--R¹) are to be prepared in a one-pot reaction, at least 2 moles ofsulphonyl halide or sulphonic anhydride (III) are to be employed permole of aminoazole (II).

The reactants can be combined in any desired sequence. In a preferredembodiment of the process according to the invention, the startingsubstances of the formulae (II) and (III) are stirred at roomtemperature with a diluent, the mixture is cooled, if appropriate, andthe acid acceptor is slowly metered into this mixture. The reactionmixture is then stirred until the reaction is complete.

If appropriate, the mixture is concentrated and/or diluted with avirtually water-immiscible organic solvent, such as, for example,methylene chloride, and working up can be carried out in a customarymanner, for example by washing with water, drying, filtering andcarefully removing the solvent from the filtrate by distillation. Thecrude product which remains in the residue can be purified further in acustomary manner, for example by column chromatography and/orrecrystallization.

The compounds which can be obtained as described above, of the formula(I) in which R² stands for the grouping --SO₂ --R¹, can be reacted togive compounds of the formula (I) in which R² stands for hydrogen by areaction with desulphonylating agents, if appropriate in the presence ofdiluents.

In this connections, desulphonylating agents are taken to meansubstances which are able to eliminate a sulphonyl grouping fromN,N-bis-sulphonyl-amino compounds. Suitable desulphonylation agents are,above all, alkali metal hydroxides or alkaline earth metal hydroxides,such as sodium hydroxide, potassium hydroxide and calcium hydroxide,alkali metal alkoxides, such as sodium methoxide, potassium methoxide,sodium ethoxide and potassium ethoxide, furthermore ammonia,alkylamines, such as methylamine, ethylamine, propylamine andbutylamine, and also dialkylamines, such as dimethylamine anddiethylamine. Ammonia is preferably employed as a desulphonylatingagent.

The desulphonylation is preferably carried out in the presence ofdiluents. Apart from water, preferred diluents are polar organicsolvents, such as methanol, ethanol, propanol, isopropanol,2-methoxyethanol, 2-ethoxyethanol and dioxane.

The desulphonylation is generally carried out at temperatures from 0° C.to 150° C., preferably at temperatures from 20° C. to 100° C.

For desulphonylation, the reactants are generally mixed at roomtemperature and, if appropriate, stirred at an increased temperatureuntil the reaction is complete. If appropriate for working up, themixture is concentrated, diluted with water and acidified with a strongacid, such as, for example, hydrochloric acid. During this process, theproduct (I, R² =H) is obtained in the form of crystals and can beisolated by filtering off with suction.

Formulae (IVA) and (IVB) provide general definitions of thesulphonylated aminoguanidines to be used as starting substances inprocess (b) according to the invention for the preparation of compoundsof the formula (I).

In the formulae (IVA) and (IVB), R¹, R⁴, X, Y and Z preferably, or inparticular, have those meanings which have already been preferablymentioned above, or mentioned above as particularly preferred, for R¹,R⁴, X, Y and Z in connection with the description of the compounds ofthe formula (I) according to the invention.

Examples of the starting substances of the formulae (IVA) and (IVB) arelisted in Table 3 below.

The meanings of the variables R¹, R⁴, X, Y and Z, each of which isindicated line by line for individual examples, in each individual casestand for the isomers of the formulae (IVA) and (IVB).

                  TABLE 3                                                         ______________________________________                                        Examples of the compounds of the formulae (IVA)                               and (IVB)                                                                     R.sup.1         R.sup.4  X     Y    Z                                         ______________________________________                                         ##STR52##      CH.sub.3 N     CH   CCH.sub.3                                  ##STR53##      CH.sub.3 N     CH   CCH.sub.3                                  ##STR54##      CH.sub.3 N     CH   CCH.sub.3                                  ##STR55##      CH.sub.3 N     CH   CCH.sub.3                                  ##STR56##      CH.sub.3 N     CH   CCH.sub.3                                  ##STR57##      CH.sub.3 N     CH   CCH.sub.3                                  ##STR58##      CH.sub.3 N     CH   CCH.sub.3                                  ##STR59##      CH.sub.3 N     CH   CCH.sub.3                                  ##STR60##      CH.sub.3 N     CH   CCH.sub. 3                                 ##STR61##      CH.sub.3 N     CH   CCH.sub.3                                  ##STR62##      CH.sub.3 N     CH   CCH.sub.3                                  ##STR63##      CH.sub.3 N     CH   CCH.sub.3                                  ##STR64##      CH.sub.3 N     CH   CCH.sub.3                                  ##STR65##      CH.sub.3 N     CH   CCH.sub.3                                  ##STR66##      CH.sub.3 N     CH   CCH.sub.3                                  ##STR67##      CH.sub.3 N     CH   COCH.sub.3                                 ##STR68##      CH.sub.3 N     CH   COCH.sub.3                                 ##STR69##      CH.sub.3 N     CH   COCH.sub.3                                 ##STR70##      CH.sub.3 N     CH   COCH.sub.3                                 ##STR71##      CH.sub.3 N     CH   COCH.sub.3                                 ##STR72##      CH.sub.3 N     CH   COCH.sub.3                                 ##STR73##      CH.sub.3 N     CH   COCH.sub.3                                 ##STR74##      CH.sub.3 N     CH   COCH.sub.3                                 ##STR75##      CH.sub.3 N     CH   COCH.sub.3                                 ##STR76##      CH.sub.3 N     CH   COCH.sub.3                                 ##STR77##      CH.sub.3 N     CH   COCH.sub.3                                 ##STR78##      CH.sub.3 N     CH   COCH.sub.3                                 ##STR79##      CH.sub.3 N     CH   COCH.sub.3                                 ##STR80##      OCH.sub.3                                                                              N     CH   C OCH.sub.3                                ##STR81##      OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR82##      OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR83##      OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR84##      OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR85##      OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR86##      OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR87##      OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR88##      OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR89##      OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR90##      OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR91##      OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR92##      OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR93##      OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR94##      OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR95##      OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR96##      OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR97##      OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR98##      CF.sub.3 N     CH   COCH.sub.3                                 ##STR99##      CF.sub.3 N     CH   COCH.sub.3                                 ##STR100##     CF.sub.3 N     CH   COCH.sub.3                                 ##STR101##     CF.sub.3 N     CH   COCH.sub.3                                 ##STR102##     CF.sub.3 N     CH   COCH.sub.3                                 ##STR103##     CF.sub.3 N     CH   COCH.sub.3                                 ##STR104##     CF.sub.3 N     CH   COCH.sub.3                                 ##STR105##     CF.sub.3 N     CH   COCH.sub.3                                 ##STR106##     CF.sub.3 N     CH   COCH.sub.3                                 ##STR107##     CF.sub.3 N     CH   COCH.sub.3                                 ##STR108##     CF.sub.3 N     CH   COCH.sub.3                                 ##STR109##     CF.sub.3 N     CH   COCH.sub.3                                 ##STR110##     CF.sub.3 N     CH   COCH.sub.3                                 ##STR111##     CF.sub.3 N     CH   COCH.sub.3                                 ##STR112##     CF.sub.3 N     CH   COCH.sub.3                                 ##STR113##     CF.sub.3 N     CH   COCH.sub.3                                 ##STR114##     CH.sub.3 N     CH   COCH.sub.3                                 ##STR115##     CH.sub.3 N     CH   COCH.sub.3                                 ##STR116##     OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR117##     OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR118##     OCH.sub.3                                                                              N     CH   CCl                                        ##STR119##     OCH.sub.3                                                                              N     CH   CCl                                        ##STR120##     OCH.sub.3                                                                              N     CH   CCl                                        ##STR121##     OCH.sub.3                                                                              N     CH   CCl                                        ##STR122##     OCH.sub.3                                                                              N     CH   CCl                                        ##STR123##     OCH.sub.3                                                                              N     CH   CCl                                        ##STR124##     OCH.sub.3                                                                              N     CH   CCl                                        ##STR125##     OCH.sub.3                                                                              N     CH   CCl                                        ##STR126##     OCH.sub.3                                                                              N     CH   CCl                                        ##STR127##     OCH.sub.3                                                                              N     CH   CCl                                        ##STR128##     OCH.sub.3                                                                              N     CH   CCl                                        ##STR129##     OCH.sub.3                                                                              N     CH   CCl                                        ##STR130##     OCH.sub.3                                                                              N     CH   CCl                                        ##STR131##     OCH.sub.3                                                                              N     CH   CCl                                        ##STR132##     OCH.sub.3                                                                              N     CH   CCl                                        ##STR133##     OCH.sub.3                                                                              N     CH   CCl                                        ##STR134##     CH.sub.3 N     CH   COCHF.sub.2                                ##STR135##     CH.sub.3 N     CH   COCHF.sub.2                                ##STR136##     CH.sub.3 N     CH   COCHF.sub.2                                ##STR137##     CH.sub.3 N     CH   COCHF.sub.2                                ##STR138##     CH.sub.3 N     CH   COCHF.sub.2                                ##STR139##     CH.sub.3 N     CH   COCHF.sub.2                                ##STR140##     CH.sub.3 N     CH   COCHF.sub.2                                ##STR141##     CH.sub.3 N     CH   COCHF.sub.2                                ##STR142##     CH.sub.3 N     CH   COCHF.sub.2                                ##STR143##     CH.sub.3 N     CH   COCHF.sub.2                                ##STR144##     OCH.sub.3                                                                              N     CH   CCl                                        ##STR145##     OCH.sub.3                                                                              N     CH   COCHF.sub.2                                ##STR146##     CH.sub.3 N     CH   COCHF.sub.2                                ##STR147##     CH.sub.3 N     CH   COCHF.sub.2                                ##STR148##     CH.sub.3 N     CH   COCHF.sub.2                                ##STR149##     OCH.sub.3                                                                              N     CH   COCHF.sub.2                                ##STR150##     OCH.sub.3                                                                              N     CH   COCHF.sub.2                                ##STR151##     OCH.sub.3                                                                              N     CH   COCHF.sub.2                                ##STR152##     OCH.sub.3                                                                              N     CH   COCHF.sub.2                                ##STR153##     OCH.sub.3                                                                              N     CH   COCHF.sub.2                                ##STR154##     OCH.sub.3                                                                              N     CH   COCHF.sub.2                                ##STR155##     OCH.sub.3                                                                              N     CH   COCHF.sub.2                                ##STR156##     OCH.sub.3                                                                              N     CH   COCHF.sub.2                                ##STR157##     OCH.sub.3                                                                              N     CH   COCHF.sub.2                                ##STR158##     OCH.sub.3                                                                              N     CH   COCHF.sub.2                                ##STR159##     OCH.sub.3                                                                              N     CH   C OCHF.sub.2                               ##STR160##     OCH.sub.3                                                                              N     CH   COCHF.sub.2                                ##STR161##     OCH.sub.3                                                                              N     CH   COCHF.sub.2                                ##STR162##     OCHF.sub.2                                                                             N     CH   COCHF.sub.2                                ##STR163##     OCHF.sub.2                                                                             N     CH   COCHF.sub.2                                ##STR164##     OCHF.sub.2                                                                             N     CH   COCHF.sub.2                                ##STR165##     OCHF.sub.2                                                                             N     CH   COCHF.sub.2                                ##STR166##     OCHF.sub.2                                                                             N     CH   COCHF.sub.2                                ##STR167##     OCHF.sub.2                                                                             N     CH   COCHF.sub.2                                ##STR168##     OCHF.sub.2                                                                             N     CH   COCHF.sub.2                                ##STR169##     OCHF.sub.2                                                                             N     CH   COCHF.sub.2                                ##STR170##     OCHF.sub.2                                                                             N     CH   COCHF.sub.2                                ##STR171##     OCHF.sub.2                                                                             N     CH   COCHF.sub.2                                ##STR172##     OCHF.sub.2                                                                             N     CH   COCHF.sub.2                                ##STR173##     OCHF.sub.2                                                                             N     CH   COCHF.sub.2                                ##STR174##     OCHF.sub.2                                                                             N     CH   COCHF.sub.2                                ##STR175##     OCHF.sub.2                                                                             N     CH   COCHF.sub.2                                ##STR176##     OCHF.sub.2                                                                             N     CH   COCHF.sub.2                                ##STR177##     OCHF.sub.2                                                                             N     CH   COCHF.sub.2                                ##STR178##     OCHF.sub.2                                                                             N     CH   COCHF.sub.2                                ##STR179##     OCHF.sub.2                                                                             N     CH   COCHF.sub.2                                ##STR180##     CH.sub.3 N     N    CCH.sub.3                                  ##STR181##     CH.sub.3 N     N    CCH.sub.3                                  ##STR182##     CH.sub.3 N     N    CCH.sub.3                                  ##STR183##     CH.sub.3 N     N    COCH.sub.3                                 ##STR184##     CH.sub.3 N     N    COCH.sub.3                                 ##STR185##     CH.sub.3 N     N    COCH.sub.3                                 ##STR186##     CH.sub.3 N     N    COCH.sub.3                                 ##STR187##     CH.sub.3 N     N    COCH.sub.3                                 ##STR188##     CH.sub.3 N     N    COCH.sub.3                                 ##STR189##     CH.sub.3 N     N    COCH.sub.3                                 ##STR190##     CH.sub.3 N     N    COCH.sub.3                                 ##STR191##     CH.sub.3 N     N    COCH.sub.3                                 ##STR192##     CH.sub.3 N     N    COCH.sub.3                                 ##STR193##     CH.sub.3 N     N    COCH.sub.3                                 ##STR194##     CH.sub.3 N     N    COCH.sub.3                                 ##STR195##     CH.sub.3 N     N    COCH.sub.3                                 ##STR196##     CH.sub.3 N     N    COCH.sub.3                                 ##STR197##     CH.sub.3 N     N    COCH.sub.3                                 ##STR198##     CH.sub.3 N     N    COCH.sub.3                                 ##STR199##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR200##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR201##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR202##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR203##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR204##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR205##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR206##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR207##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR208##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR209##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR210##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR211##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR212##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR213##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR214##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR215##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR216##     C.sub.2 H.sub.5                                                                        N     N    COCH.sub.3                                 ##STR217##     CH.sub.3 N     N    COC.sub.2 H.sub. 5                         ##STR218##     OCH.sub.3                                                                              N     N    CNHC.sub.2 H.sub.5                         ##STR219##     OC.sub.2 H.sub.5                                                                       N     N    CNHCH.sub.3                                ##STR220##     OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR221##     OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR222##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR223##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR224##     OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR225##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR226##     OCH.sub.3                                                                              N     N    COCH.sub.3                                 ##STR227##     OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR228##     OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR229##     OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR230##     OCH.sub.3                                                                              N     CH   COCH.sub.3                                 ##STR231##     OCH.sub.3                                                                              N     N    COCH.sub.3                                ______________________________________                                    

Some of the sulphonylated aminoguanidines of the formula (IVA) aredisclosed in EP-A 224,078 and U.S. Pat. No. 4,725,303, and some of themform the subject of a German Patent Application P 3,818,040.5 filed May27, 1988.

The compounds of the general formula (IVA) are obtained when sulphonylcompounds of the general formula (XIII) ##STR232## in which R¹, R⁴, X, Yand Z have the abovementioned meanings and

Q⁴ stands for halogen or for one of the leaving groups ##STR233## whichare indicated below, wherein R³⁴ has the meaning mentioned above for R¹,but is not necessarily identical to R¹ in each individual case,

R³⁵ stands for alkyl, alkenyl or aralkyl,

R³⁶ stands for in each case optionally substituted alkyl, aralkyl oraryl and

Q⁵ stands for oxygen or sulphur

with hydrazine or a hydrazine/water adduct or hydrazine/acid adduct, ifappropriate in the presence of an acid acceptor, such as, for example,potassium carbonate, and if appropriate in the presence of a diluent,such as, for example, methanol, ethanol and/or water, at temperaturesfrom -20° C. to +100° C.

Some of the compounds of the formula (IVA) can also be obtained asoutlined below (R as mentioned above for R¹⁰) ##STR234## (for theprinciple of the reaction, cf. U.S. Pat. No. 4,659,364, EP-A 173,319).

Formula (XIII) provides a general definition of the sulphonyl compoundsrequired as intermediates. In formula (XIII), R¹, R⁴, X, Y and Zpreferably, or in particular, have those meanings which have alreadybeen preferably mentioned above, or mentioned above as particularlypreferred, for R¹, R⁴, X, Y and Z in context with the description of thecompounds of the formula (I) according to the invention and Q⁴preferably stands for chlorine or one of the leaving groups ##STR235##mentioned below, wherein R³⁴ has the meaning preferably given above forR¹, but is not necessarily identical to R¹ in each individual case,

R³⁵ stands for C₁ -C₄ -alkyl, C₃ -C₄ -alkenyl or benzyl,

R³⁶ stands for C₁ -C₄ -alkyl which is optionally substituted bycarboxyl, C₁ -C₄ -alkoxycarbonyl or C₁ -C₄ -alkoxy or for benzyl orphenyl, each of which is optionally substituted by fluorine, chlorine,bromine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, and

Q⁵ stands for oxygen or sulphur.

Examples of the compounds of the formula (XIII) are listed in Table 4below.

                                      TABLE 4                                     __________________________________________________________________________    Examples of the compounds of the formula (XIII)                               Q.sup.4           R.sup.1       R.sup.4                                                                            X Y  Z                                   __________________________________________________________________________     ##STR236##                                                                                      ##STR237##   CH.sub.3                                                                           N CH COCH.sub.3                           ##STR238##                                                                                      ##STR239##   OCH.sub.3                                                                          N CH COCH.sub.3                           ##STR240##                                                                                      ##STR241##   OCH.sub.3                                                                          N CH COCH.sub.3                           ##STR242##                                                                                      ##STR243##   OCH.sub.3                                                                          N CH COCH.sub.3                           ##STR244##                                                                                      ##STR245##   OCH.sub.3                                                                          N CH COCH.sub.3                           ##STR246##                                                                                      ##STR247##   OCH.sub.3                                                                          N CH COCH.sub.3                           ##STR248##                                                                                      ##STR249##   CH.sub.3                                                                           N CH CCH.sub.3                            ##STR250##                                                                                      ##STR251##   CH.sub.3                                                                           N CH CCH.sub.3                            ##STR252##                                                                                      ##STR253##   OCH.sub.3                                                                          N CH COCH.sub.3                           ##STR254##                                                                                      ##STR255##   OCH.sub.3                                                                          N CH COCH.sub.3                           ##STR256##                                                                                      ##STR257##   C.sub.2 H.sub.5                                                                    N CH COCH.sub.3                           ##STR258##                                                                                      ##STR259##   C.sub.2 H.sub.5                                                                    N CH COCH.sub.3                           ##STR260##                                                                                      ##STR261##   OCH.sub.3                                                                          N CH CCl                                  ##STR262##                                                                                      ##STR263##   OCH.sub.3                                                                          N CH CCl                                  ##STR264##                                                                                      ##STR265##   OCH.sub.3                                                                          N CH CCl                                  ##STR266##                                                                                      ##STR267##   OCH.sub.3                                                                          N CH CCl                                  ##STR268##                                                                                      ##STR269##   H    N CH CCH.sub.3                            ##STR270##                                                                                      ##STR271##   CH.sub.3                                                                           N CH COCH.sub.3                           ##STR272##                                                                                      ##STR273##   OCH.sub.3                                                                          N CH C OCH.sub.3                          ##STR274##                                                                                      ##STR275##   CH.sub.3                                                                           N CH COCH.sub.3                           ##STR276##                                                                                      ##STR277##   OCH.sub.3                                                                          N CH COCH.sub.3                           ##STR278##                                                                                      ##STR279##   OCH.sub.3                                                                          N CH COCH.sub.3                           ##STR280##                                                                                      ##STR281##   CH.sub.3                                                                           N CH COC.sub.2 H.sub.5                    ##STR282##                                                                                      ##STR283##   OCHF.sub.2                                                                         N CH CCH.sub.3                            ##STR284##                                                                                      ##STR285##   CH.sub.3                                                                           N CH CSCH.sub.3                           ##STR286##                                                                                      ##STR287##   CH.sub.3                                                                           N CH CN(CH.sub.3).sub.2                   ##STR288##                                                                                      ##STR289##   OCHF.sub.2                                                                         N CH COCHF.sub.2                          ##STR290##                                                                                      ##STR291##   OCH.sub.3                                                                          N CH COCH.sub.3                           ##STR292##                                                                                      ##STR293##   OCH.sub.3                                                                          N N  COCH.sub.3                           ##STR294##                                                                                      ##STR295##   CH.sub.3                                                                           N N  COCH.sub.3                           ##STR296##                                                                                      ##STR297##   OCH.sub.3                                                                          N N  COCH.sub.3                           ##STR298##                                                                                      ##STR299##   OCH.sub.3                                                                          N N  COCH.sub.3                           ##STR300##                                                                                      ##STR301##   CH.sub.3                                                                           N N  COCH.sub.3                           ##STR302##                                                                                      ##STR303##   OCH.sub.3                                                                          N N  COCH.sub.3                           ##STR304##                                                                                      ##STR305##   CH.sub.3                                                                           N N  CCH.sub.3                            ##STR306##                                                                                      ##STR307##   CH.sub.3                                                                           N N  CCl                                  ##STR308##                                                                                      ##STR309##   OCH.sub.3                                                                          N N  COCH.sub.3                           ##STR310##                                                                                      ##STR311##   OCH.sub.3                                                                          N N  COCH.sub.3                           ##STR312##                                                                                      ##STR313##   OCH.sub.3                                                                          N N  COCH.sub.3                           ##STR314##                                                                                      ##STR315##   OCH.sub.3                                                                          N CH COCH.sub.3                           ##STR316##                                                                                      ##STR317##   OCH.sub.3                                                                          N CH COCH.sub.3                          OC.sub.6 H.sub.5                                                                                 ##STR318##   CH.sub.3                                                                           N CH CCH.sub.3                           OCH.sub.3                                                                                        ##STR319##   CH.sub.3                                                                           N CH COCH.sub.3                          SCH.sub.3                                                                                        ##STR320##   OCH.sub.3                                                                          N CH COCH.sub.3                          SC.sub.6 H.sub.5                                                                                 ##STR321##   OCH.sub.3                                                                          N CH COCH.sub.3                           ##STR322##                                                                                      ##STR323##   CH.sub.3                                                                           N N  COCH.sub.3                           ##STR324##                                                                                      ##STR325##   OCH.sub.3                                                                          N CH COCH.sub.3                           ##STR326##                                                                                      ##STR327##   OCH.sub.3                                                                          N CH COCH.sub.3                          Cl                                                                                               ##STR328##   OCH.sub.3                                                                          N CH COCH.sub.3                          OC.sub.6 H.sub.5                                                                                 ##STR329##   OCH.sub.3                                                                          N CH C OCH.sub.3                         SC.sub.6 H.sub.5                                                                                 ##STR330##   OCH.sub.3                                                                          N CH COCH.sub.3                          Cl                                                                                               ##STR331##   CH.sub.3                                                                           N N  COCH.sub.3                           ##STR332##                                                                                      ##STR333##   CH.sub.3                                                                           N N  COCH.sub.3                          OC.sub.6 H.sub.5                                                                                 ##STR334##   CH.sub.3                                                                           N N  COCH.sub.3                           ##STR335##                                                                                      ##STR336##   CH.sub.3                                                                           N N  COCH.sub.3                          SC.sub.6 H.sub.5                                                                                 ##STR337##   CH.sub.3                                                                           N N  COCH.sub.3                          SCH.sub.3                                                                                        ##STR338##   CH.sub.3                                                                           N N  OCH.sub.3                            ##STR339##                                                                                      ##STR340##   OCH.sub.3                                                                          N CH OCH.sub.3                           OCH.sub.3                                                                                        ##STR341##   OCH.sub.3                                                                          N N  OCH.sub.3                           __________________________________________________________________________

The compounds of the formula (XIII) are known and/or can be prepared byprocesses known per se (cf. EP-A 5,986, EP-A 24,215, EP-A 121,082, EP-A172,957, EP-A 173,321, EP-A 173,956, EP-A 224,078, DE-OS (GermanPublished Specification) 3,634,928, DE-OS (German PublishedSpecification) 3,634,929).

The sulphonylated aminoguanidines of the formula (IVB) were hithertounknown from the literature and form the subject of the presentinvention. The new sulphonylated aminoguanidines of the general formula(IVB) are obtained when their isomer compounds of the formula(IVA)--above--are rearranged by stirring with a polar solvent, such as,for example, methanol, ethanol, propanol, isopropanol and/or water, attemperatures from 0° C. to 150° C.

In order to prepare the compounds of the formula (IVB), it is alsopossible to generate the isomers of the formula (IVA) as described aboveand to rearrange them in situ, i.e., without intermediate isolation.

Formula (V) provides a general definition of the ester(amide)s also tobe used as starting substances in process (b) according to the inventionfor the preparation of compounds of the formula (I).

In formula (V), R³ preferably, or in particular, has the meaning whichhas already been preferably mentioned above, or mentioned above asparticularly preferred, for R³ in connection with the description of thecompounds of the formula (I) according to the invention, R preferablystands for C₁ -C₄ -alkyl, in particular for methyl or ethyl, and Q¹preferably stands for C₁ -C₄ -alkoxy or di-(C₁ -C₂ -alkyl)-amino, inparticular for methoxy, ethoxy or dimethylamino.

Examples of the starting substances of the formula (V) which may bementioned are: N,N-dimethylformamide dimethyl acetal andN,N-dimethylformamide diethyl acetal, trimethyl orthoformate andtriethyl orthoformate, trimethyl orthoacetate and triethyl orthoacetate.

The compounds of the formula (V) are known chemicals for synthesis.

Process (b) according to the invention is preferably carried out in thepresence of a diluent. In addition to the diluents indicated in process(a), alcohols, such as methanol, ethanol, propanol or isopropanol, arealso particularly suitable as diluents in process (b).

When carrying out process (b) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures from 0° C. to 150° C.,preferably at temperatures from 10° C. to 100° C.

Process (b) according to the invention is generally carried out underatmospheric pressure. However, it is also possible for the process to becarried out under increased or reduced pressure.

For carrying out process (b) according to the invention, the startingsubstances required in each case are generally employed in approximatelyequimolar amounts. However, it is also possible to use one of the twocomponents employed in each case in a relatively large excess. Thereactions are generally carried out in a suitable diluent, and thereaction mixture is stirred for several hours at the temperaturerequired in each case. Working up in process (b) according to theinvention is in each case carried out by customary methods.

Formula (VI) provides a general definition of the substitutedaminopyrazolines to be used as starting substances in process (c)according to the invention for the preparation of compounds of theformula (I).

In formula (VI), R⁴, X, Y and Z preferably, or in particular, have thosemeanings which have already been preferably described above, ordescribed above as particularly preferred, for R⁴, X, Y and Z inconnection with the description of the compounds of the formula (I)according to the invention.

Examples of the starting substances of the formula (VI) are listed inTable 5 below.

                  TABLE 5                                                         ______________________________________                                        Examples of the compounds of the formula (VI)                                 R.sup.4      X        Y         Z                                             ______________________________________                                        CH.sub.3     H        CH        C--CH.sub.3                                   CH.sub.3     N        CH        C--OCH.sub.3                                  CH.sub.3     N        CH        C--OC.sub.2 H.sub.5                           OCH.sub.3    N        CH        C--OCH.sub.3                                  OCH.sub.3    N        CH        C--Cl                                         H            N        CH        C--CH.sub.3                                   CF.sub.3     N        CH        C--OCH.sub.3                                  OCH.sub.3    N        CH        C--OCHF.sub.2                                 CH.sub.3     N        CH        C--OCHF.sub.2                                 OCHF.sub.2   N        CH        C--OCHF.sub.2                                 CH.sub.3     N        N         C--CH.sub.3                                   CH.sub.3     N        N         C--OCH.sub.3                                  OCH.sub.3    N        N         C--OCH.sub.3                                  C.sub.2 H.sub.5                                                                            N        CH        C--OCH.sub.3                                  C.sub.2 H.sub.5                                                                            N        N         C--OCH.sub.3                                  ______________________________________                                    

The starting substances of the formula (VI) were hitherto unknown fromthe literature. The compounds of the formula (VI) are obtained whenhydrazinoazines of the formula (IX) ##STR342## in which R⁴, X, Y and Zhave the abovementioned meanings,

are reacted with acrylonitrile in the presence of a base, such as, forexample, sodium methoxide, potassium methoxide, sodium ethoxide and/orpotassium ethoxide, and in the presence of a diluent, such as, forexample, methanol and/or ethanol, at temperatures from 0° C. to 100° C.

Furthermore, process (c) according to the invention is carried out usingsulphonyl halides or sulphonic anhydrides (III). As far as the startingsubstances for process (c) are concerned, the data of the compounds ofthe formula (III) provided above in the description of the startingsubstances of process (a) are applicable.

Process (c) according to the invention is preferably carried out usingdiluents.

Suitable diluents are virtually all inert organic solvents, as they havebeen mentioned above in process (a) according to the invention.

If appropriate, process (c) is carried out in the presence of an acidacceptor. Suitable acid-binding agents are above all those which havebeen mentioned above in process (a).

When carrying out process (c) according to the invention, the reactiontemperatures can be varied within a relatively wide range. In general,the process is carried out at temperatures from -50° C. to +50° C.,preferably at temperatures from -40° C. to +40° C.

For carrying out process (c) according to the invention, 1 to 5 moles,preferably 1 to 4 moles, of sulphonyl halide or sulphonic anhydride ofthe formula (III) are generally employed per mole of aminopyrazoline ofthe formula (VI). If disulphonylated compounds of the formula (I, R²=--SO₂ --R¹) are to be prepared in a one-pot reaction, at least 2 molesof sulphonyl halide or sulphonic anhydride (III) are to be employed permole of aminopyrazoline (VI).

The reactants can be combined in any desired sequence. In a preferredembodiment of process (c) according to the invention, the startingsubstances of the formulae (VI) and (III) are stirred at roomtemperature with a diluent, the mixture is cooled, if appropriate, andthe acid acceptor is slowly metered into this mixture. The reactionmixture is then stirred until the reaction is complete.

Working up and (if appropriate) desulphonylation can be carried out asdescribed above in process (a).

If desired, salts can be prepared from the compounds of the generalformula (I) according to the invention. Such salts are obtained in asimple manner by customary salt formation methods, for example bydissolving or dispersing a compound of the formula (I) in a suitablesolvent, such as, for example, water, methanol, ethanol or acetone, andadding a suitable acid or base. If appropriate, the mixture is stirredfor a relatively long time, and the salts can then be isolated byconcentrating or filtering off with suction.

The active compounds according to the invention can be used asdefoliants, desiccants, agents for destroying broad-leaved plants and,especially, as weed-killers.. By weeds, in the broadest sense, there areto be understood all plants which grow in locations where they areundesired. Whether the substances according to the invention act astotal or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio,Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala,Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver and Centaurea.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus andAllium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The compounds are suitable, depending on the concentration, for thetotal combating of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be employed for combating weeds in perennialcultures, for example forests, decorative tree plantings, orchards,vineyards, citrus groves, nut orchards, banana platations, coffeeplantations, tea plantations, rubber plantations, oil palm plantations,cocoa plantations, soft fruit plantings and hop fields, and for theselective combating of weeds in annual cultures.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and very fine capsules in polymeric substances.

These formulations are produced in known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surface-active agents, thatis emulsifying agents and/or dispersing agents and/or foam-formingagents.

In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. As liquid solvents,there are suitable in the main: aromatics, such as xylene, toluene oralkyl naphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample petroleum fractions, mineral and vegetable oils, alcohols, suchas butanol or glycol as well as their ethers and esters, ketones, suchas acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water.

As solid carriers there are suitable: for example ammonium salts andground natural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly disperse silicic acid, alumina and silicates,as solid carriers for granules there are suitable: for example crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, corn cobs and tobacco stalks; as emulsifying and/or foam-formingagents there are suitable: for example non-ionic and anionicemulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well asalbumin hydrolysis products; as dispersing agents there are suitable:for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Further additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in the formof their formulations, can also be used, for combating weeds, asmixtures with known herbicides, finished formulations or tank mixesbeing possible.

Possible components for the mixtures are known herbicides, such as, forexample,1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dione(AMETHYDIONE) or N-(2-benzothiazolyl)-N,N'-dimethyl-urea(METABENZTHIAZURON) for combating weeds in cereals;4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) forcombating weeds in sugar beets and4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one(METRIBUZIN) for combating weeds in soy beans; furthermore also2,4-dichlorophenoxyacetic acid (2,4-D); 4-(2,4-dichlorophenoxy)butyricacid (2,4-DB); 2,4-dichlorophenoxypropionic acid (2,4-DP);5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoic acid(ACIFLUORFEN); N-(methoxymethyl)-2,6-diethyl-chloroacetanilide(ALACHLOR); methyl 4-aminobenzenesulfonylcarbamate (ASULAM);2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine (ATRAZIN);3-isopropyl-2,1,3-benzothiadiazin-4-one 2,2-dioxide (BENTAZONE); methyl5-(2,4-dichlorophenoxy)-2-nitrobenzoate (BIFENOX);3,5-dibromo-4-hydroxy-benzonitrile (BROMOXYNIL);2,6-dichlorobenzonitrile (DICHLOBENIL);2-[(2-chlorophenyl)-methyl]-4,4-dimethylisoxazolidin-3-one(DIMETHAZONE); 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one(ETHIOZIN); 2-{4-[(6-chloro-2-benzoxazolyl)-oxy]-phenoxy}-propanoicacid, its methyl ester or its ethyl ester (FENOXAPROP);N,N-dimethyl-N'-(3-trifluoromethylphenyl)-urea (FLUOMETURON);[(4-amino-3,5-dichloro- 6-fluoro-2-pyridinyl)-oxy]-acetic acid or its1-methylheptyl ester (FLUOROXYPYR);5-(2-chloro-4-trifluoromethyl-phenoxy)-N-methylsulphonyl-2-nitrobenzamide(FOMESAFEN); N-phosphonomethyl-glycine (GLYPHOSATE);2-{4-[(3-chloro-5-(trifluoromethyl)-2-pyridinyl)-oxy]phenoxy}-propanoicacid or its ethyl ester (HALOXYFOP);3-cyclohexyl-6-dimethylamino-1-methyl-1,3,5-triazin-2,4-dione(HEXAZINONE); methyl2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-4(5)-methylbenzoate(IMAZAMETHABENZ);2-(4,5-dihydro-4-methyl-4-isopropyl-5-oxo-1H-imidazol-2-yl)-pyridin-3-carboxylicacid (IMAZAPYR);2-[5-methyl-5-(1-methylethyl)-4-oxo-2-imidazolin-2-yl]-3-quinolinecarboxylicacid (IMAZAQUIN);2-[4,5-dihydro-4-methyl-4-isopropyl-5-oxo-(1H)-imidazol-2-yl]-5-ethyl-pyridine-3-carboxylicacid (IMAZETHAPYR); 3,5-diiodo-4-hydroxybenzonitrile (IOXYNIL);N,N-dimethyl-N'-(4-isopropylphenyl)-urea (ISOPROTURON);(2-ethoxy-1-methyl-2-oxo-ethyl)-5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate(LACTOFEN); (2-methyl-4-chlorophenoxy)-acetic acid (MCPA);(4-chloro-2-methylphenoxy)propionic acid (MCPP);N-methyl-2-(1,3-benzothiazol-2-yloxy)-acetanilide (MEFENACET);2-ethyl-6-methyl-N-(1-methyl-2-methoxyethyl)-chloroacetanilide(METOLACHLOR); N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitroaniline(PENDIMETHALIN); 4-amino-3,5,6-trichloropyridine-2-carboxylic acid(PICLORAM);2-[1-(ethoxamino)-butylidene]-5-(2-ethylthiopropyl)-1,3-cyclohexadione(SETHOXYDIM); 2-chloro-4,6-bis-(ethylamino)-1,3,5-triazine (SIMAZIN);methyl2-{[(4,6-dimethyl-2-pyrimidinyl)-aminocarbonyl]aminosulphonyl}-benzoate(SULFOMETURON) and 2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline(TRIFLURALIN). Surprisingly, some mixtures also show a synergisticaction.

Mixtures with other known active compounds, such as fungicides,insecticides, acaricides, nematicides, bird repellents, plant nutrientsand agents which improve soil structure, are also possible.

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are used in the customary manner, for example bywatering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied eitherbefore or after emergence of the plants.

They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a substantial range.It depends essentially on the nature of the desired effect. In general,the amounts used are between 0.01 and 10 kg of active compound perhectare of soil surface, preferably between 0.05 and 5 kg per ha.

The preparation and use of the active compounds according to theinvention can be seen from the following examples.

PREPARATION EXAMPLES EXAMPLE 1 (IA-1) ##STR343##

26.1 g (0.1 mol) of methyl 2-chlorosulphonylbenzoate are added to asolution of 4.75 g (0.025 mol) of1-(4,6-dimethyl-pyrimidin-2-yl)-3-amino-triazole in 100 ml of methylenechloride, the mixture is cooled to -5° C., and 11.2 g (0.1 mol) ofdiazabicyclo[2.2.2]octane, dissolved in 40 ml of methylene chloride, areadded dropwise at -5° C. to 0° C. The reaction mixture is stirred for 2days at room temperature (20° C.) and then washed with water; themethylene chloride phase is separated off, dried over sodium sulphate,filtered and concentrated. The oily residue can be crystallized usingethyl acetate.

The residue is filtered off with suction and dried, and 6.6 g (45% oftheory) of1-(4,6-dimethylpyrimidin-2-yl)-3-(N,N-bis-(2-methoxycarbonyl-phenylsulphonyl))-aminotriazoleremain as colorless crystals of melting point 209°-212° C.

EXAMPLE 2 (IA-2) ##STR344##

1.17 g (0.002 mol) of1-(4,6-dimethyl-pyrimidin-2-yl)-3-(N,N-bis-(2-methoxycarbonyl-phenylsulphonyl))aminotriazoleare stirred at reflux temperature (about 70° C.) overnight in a mixtureof 10 ml of 25% strength ammonia water and 10 ml of ethanol. In thisprocess, the substance dissolves completely. The batch is concentratedand the residue is diluted with 30 ml of water. A pH of 3 is adjustedwith hydrochloric acid and the product is filtered off with suction,washed and dried.

0.7 g (90% of theory) of1-(4,6-dimethyl-pyrimidin-2-yl)-3-(2-methoxycarbonyl-phenylsulphonyl)aminotriazolein the form of colorless crystals of melting point 215° C.-217° C. isobtained.

The compounds of the formula (I), which is specified in more detail byformulae (IA), (IB) and (IC), which are listed in Table 2 below can beprepared in analogy to Examples 1 and 2 and following the generaldescription of the process according to the invention: ##STR345##

(In Table 6 below, A is indicated in each case instead of A').

    __________________________________________________________________________    Example                                                  Melting              No.   A  R.sup.1      R.sup.2      R.sup.3                                                                           R.sup.4                                                                            X Y  Z       Point                                                                         (°C.)         __________________________________________________________________________    IA-3  N                                                                                 ##STR346##  Na           H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             111                  IA-4  N                                                                                 ##STR347##  K            H   CH.sub.3                                                                           N CH CCH.sub.3                    IA-5  N                                                                                 ##STR348##                                                                                 ##STR349##  H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             165                  IA-6  N                                                                                 ##STR350##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             202                  IA-7  N                                                                                 ##STR351##                                                                                 ##STR352##  H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             229                  IA-8  N                                                                                 ##STR353##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             240                  IA-9  N                                                                                 ##STR354##                                                                                 ##STR355##  H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             152                  IA-10 N                                                                                 ##STR356##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             190                  IB-11 N                                                                                 ##STR357##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             204                  IA-12 N                                                                                 ##STR358##                                                                                 ##STR359##  H   CH.sub.3                                                                           N CH CCH.sub.3                    IA-13 N                                                                                 ##STR360##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             89                   IA-14 N                                                                                 ##STR361##                                                                                 ##STR362##  H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             246                  IA-15 N                                                                                 ##STR363##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             269                  IA-16 N                                                                                 ##STR364##                                                                                 ##STR365##  H   CH.sub.3                                                                           N CH CCH.sub.3                    IA-17 N                                                                                 ##STR366##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                    IA-18 N                                                                                 ##STR367##                                                                                 ##STR368##  H   CH.sub.3                                                                           N CH CCH.sub.3                    IA-19 N                                                                                 ##STR369##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                    IA-20 N                                                                                 ##STR370##                                                                                 ##STR371##  H   CH.sub.3                                                                           N CH CCH.sub.3                    IA-21 N                                                                                 ##STR372##                                                                                 ##STR373##  H   CH.sub.3                                                                           N N  CCH.sub.3                    IA-22 N                                                                                 ##STR374##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             230                  IA-23 N                                                                                 ##STR375##                                                                                 ##STR376##  H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             202                  IA-24 N                                                                                 ##STR377##                                                                                 ##STR378##  H   CH.sub.3                                                                           N CH CCH.sub.3                    IA-25 N                                                                                 ##STR379##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             211                  IA-26 N                                                                                 ##STR380##  H            H   CH.sub. 3                                                                          N CH CCH.sub.3                    IA-27 N                                                                                 ##STR381##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             203                  IA-28 N                                                                                 ##STR382##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                    IA-29 N                                                                                 ##STR383##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                    IA-30 N                                                                                 ##STR384##                                                                                 ##STR385##  H   CH.sub.3                                                                           N CH COCH.sub.3                   IA-31 N                                                                                 ##STR386##  H            H   CH.sub.3                                                                           N CH COCH.sub.3                                                                            225                  IA-32 N                                                                                 ##STR387##                                                                                 ##STR388##  H   CH.sub.3                                                                           N CH COCH.sub.3                                                                            214                  IA-33 N                                                                                 ##STR389##  H            H   CH.sub.3                                                                           N CH COCH.sub.3                                                                            167                  IA-34 N                                                                                 ##STR390##                                                                                 ##STR391##  H   CH.sub.3                                                                           N CH COCH.sub.3                   IA-35 N                                                                                 ##STR392##  H            H   CH.sub.3                                                                           N CH COCH.sub.3                   IA-36 N                                                                                 ##STR393##  H            H   CH.sub.3                                                                           N CH COCH.sub.3                   IA-37 N                                                                                 ##STR394##  H            H   CH.sub.3                                                                           N CH COCH.sub.3                   IA-38 N                                                                                 ##STR395##                                                                                 ##STR396##  H   CH.sub.3                                                                           N CH COCH.sub.3                   IA-39 N                                                                                 ##STR397##                                                                                 ##STR398##  H   CH.sub.3                                                                           N CH COCH.sub.3                   IA-40 N                                                                                 ##STR399##                                                                                 ##STR400##  H   CH.sub.3                                                                           N CH COCH.sub.3                   IA-41 N                                                                                 ##STR401##  H            H   CH.sub.3                                                                           N CH COCH.sub.3                   IA-42 N                                                                                 ##STR402##                                                                                 ##STR403##  H   CH.sub.3                                                                           N CH COCH.sub.3                   IA-43 N                                                                                 ##STR404##  H            H   CH.sub.3                                                                           N CH COCH.sub.3                   IA-44 N                                                                                 ##STR405##                                                                                 ##STR406##  H   CH.sub.3                                                                           N CH COCH.sub.3                   IA-45 N                                                                                 ##STR407##  H            H   CH.sub.3                                                                           N CH COCH.sub.3                                                                            223                  IA-46 N                                                                                 ##STR408##                                                                                 ##STR409##  H   CH.sub.3                                                                           N CH COCH.sub.3                   IA-47 N                                                                                 ##STR410##  H            H   CH.sub.3                                                                           N CH COCH.sub.3                                                                            244                  IA-48 N                                                                                 ##STR411##  H            H   CH.sub.3                                                                           N CH COCH.sub.3                   IA-49 N                                                                                 ##STR412##  H            H   CH.sub.3                                                                           N CH COCH.sub.3                                                                            168                  IA-50 N                                                                                 ##STR413##  H            H   CH.sub.3                                                                           N CH COCH.sub.3                   IA-51 N                                                                                 ##STR414##                                                                                 ##STR415##  H   OCH.sub.3                                                                          N CH COCH.sub.3                                                                            208                  IA-52 N                                                                                 ##STR416##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                                                                            203                  IA-53 N                                                                                 ##STR417##                                                                                 ##STR418##  H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-54 N                                                                                 ##STR419##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-55 N                                                                                 ##STR420##                                                                                 ##STR421##  H   OCH.sub.3                                                                          N CH COCH.sub.3                                                                            195                  IA-56 N                                                                                 ##STR422##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-57 N                                                                                 ##STR423##                                                                                 ##STR424##  H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-58 N                                                                                 ##STR425##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-59 N                                                                                 ##STR426##                                                                                 ##STR427##  H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-60 N                                                                                 ##STR428##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-61 N                                                                                 ##STR429##                                                                                 ##STR430##  H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-62 N                                                                                 ##STR431##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-63 N                                                                                 ##STR432##                                                                                 ##STR433##  H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-64 N                                                                                 ##STR434##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-65 N                                                                                 ##STR435##                                                                                 ##STR436##  H   OCH.sub.3                                                                          H CH COCH.sub.3                   IA-66 N                                                                                 ##STR437##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                                                                            194                  IA-67 N                                                                                 ##STR438##                                                                                 ##STR439##  H   OCH.sub.3                                                                          N CH COCH.sub.3                                                                            190                  IA-68 N                                                                                 ##STR440##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                                                                            233                  IA-69 N                                                                                 ##STR441##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-70 N                                                                                 ##STR442##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-71 N                                                                                 ##STR443##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                                                                            203                  IA-72 N                                                                                 ##STR444##                                                                                 ##STR445##  H   CF.sub.3                                                                           N CH COCH.sub.3                   IA-73 N                                                                                 ##STR446##                                                                                 ##STR447##  H   OCH.sub.3                                                                          N CH CCl                          IA-74 N                                                                                 ##STR448##  H            H   CF.sub.3                                                                           N CH COCH.sub.3                   IA-75 N                                                                                 ##STR449##                                                                                 ##STR450##  H   CF.sub.3                                                                           N CH COCH.sub.3                   IA-76 N                                                                                 ##STR451##  H            H   CF.sub.3                                                                           N CH COCH.sub.3                   IA-77 N                                                                                 ##STR452##  H            H   CF.sub.3                                                                           N CH COCH.sub.3                   IA-78 N                                                                                 ##STR453##  H            H   OCH.sub.3                                                                          N CH CCl                          IA-79 N                                                                                 ##STR454##                                                                                 ##STR455##  H   OCH.sub.3                                                                          N CH CCl                          IA-80 N                                                                                 ##STR456##  H            H   OCH.sub.3                                                                          N CH CCl                          IA-81 N                                                                                 ##STR457##  H            H   OCH.sub.3                                                                          N CH CCl     226                  IA-82 N                                                                                 ##STR458##                                                                                 ##STR459##  H   OCH.sub.3                                                                          N CH CCl                          IA-83 N                                                                                 ##STR460##                                                                                 ##STR461##  H   OCH.sub.3                                                                          N CH CCl                          IA-84 N                                                                                 ##STR462##  H            H   OCH.sub.3                                                                          N CH CCl                          IA-85 N                                                                                 ##STR463##                                                                                 ##STR464##  H   OCH.sub.3                                                                          N CH COCHF.sub.2                  IA-86 N                                                                                 ##STR465##  H            H   OCH.sub.3                                                                          N CH COCHF.sub.2                  IA-87 N                                                                                 ##STR466##                                                                                 ##STR467##  H   OCH.sub.3                                                                          N CH COCHF.sub.2                  IA-88 N                                                                                 ##STR468##  H            H   OCH.sub.3                                                                          N CH COCHF.sub.2                  IA-89 N                                                                                 ##STR469##                                                                                 ##STR470##  H   OCH.sub.3                                                                          N CH COCHF.sub.2                  IA-90 N                                                                                 ##STR471##  H            H   OCH.sub.3                                                                          N CH COCHF.sub.2                  IA-91 N                                                                                 ##STR472##                                                                                 ##STR473##  H   OCHF.sub.2                                                                         N CH COCHF.sub.2                  IA-92 N                                                                                 ##STR474##  H            H   OCHF.sub.2                                                                         N CH COCHF.sub.2                  IA-93 N                                                                                 ##STR475##                                                                                 ##STR476##  H   OCHF.sub.2                                                                         N CH COCHF.sub.2                  IA-94 N                                                                                 ##STR477##  H            H   OCHF.sub.2                                                                         N CH COCHF.sub.2                  IA-95 N                                                                                 ##STR478##                                                                                 ##STR479##  H   OCHF.sub.2                                                                         N CH COCHF.sub.2                  IA-96 N                                                                                 ##STR480##  H            H   OCHF.sub.2                                                                         N CH COCHF.sub.2                  IA-97 N                                                                                 ##STR481##                                                                                 ##STR482##  H   OCHF.sub.2                                                                         N CH COCHF.sub.2                  IA-98 N                                                                                 ##STR483##  H            H   OCHF.sub.2                                                                         N CH COCHF.sub.2                  IA-99 N                                                                                 ##STR484##                                                                                 ##STR485##  H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-100                                                                              N                                                                                 ##STR486##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-101                                                                              N                                                                                 ##STR487##                                                                                 ##STR488##  H   OCH.sub.3                                                                          N CH CCl                          IA-102                                                                              N                                                                                 ##STR489##  H            H   OCH.sub.3                                                                          N CH CCl                          IA-103                                                                              N                                                                                 ##STR490##                                                                                 ##STR491##  H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-104                                                                              N                                                                                 ##STR492##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-105                                                                              N                                                                                 ##STR493##                                                                                 ##STR494##  H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-106                                                                              N                                                                                 ##STR495##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-107                                                                              N                                                                                 ##STR496##                                                                                 ##STR497##  H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-108                                                                              N                                                                                 ##STR498##                                                                                 ##STR499##  H   OCH.sub.3                                                                          N CH COCHF.sub.2                  IA-109                                                                              N                                                                                 ##STR500##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-110                                                                              N                                                                                 ##STR501##                                                                                 ##STR502##  H   OCH.sub.3                                                                          N CH COCHF.sub.2                  IA-111                                                                              N                                                                                 ##STR503##  H            H   CH.sub.3                                                                           N N  CCH.sub.3                    IA-112                                                                              N                                                                                 ##STR504##                                                                                 ##STR505##  H   CH.sub.3                                                                           N N  CCH.sub.3                    IA-113                                                                              N                                                                                 ##STR506##                                                                                 ##STR507##  H   CH.sub.3                                                                           N N  CCH.sub.3                    IA-114                                                                              N                                                                                 ##STR508##                                                                                 ##STR509##  H   CH.sub.3                                                                           N N  COCH.sub.3                   IA-115                                                                              N                                                                                 ##STR510##  H            H   CH.sub.3                                                                           N N  COCH.sub.3                   IA-116                                                                              N                                                                                 ##STR511##                                                                                 ##STR512##  H   CH.sub.3                                                                           N N  COCH.sub.3                   IA-117                                                                              N                                                                                 ##STR513##  H            H   CH.sub.3                                                                           N N  COCH.sub.3                   IA-118                                                                              N                                                                                 ##STR514##                                                                                 ##STR515##  H   CH.sub.3                                                                           N N  COCH.sub.3                   IA-119                                                                              N                                                                                 ##STR516##  H            H   CH.sub.3                                                                           N N  COCH.sub.3                   IA-120                                                                              N                                                                                 ##STR517##  Na           H   CH.sub.3                                                                           N N  COCH.sub.3                   IA-121                                                                              N                                                                                 ##STR518##                                                                                 ##STR519##  H   CH.sub.3                                                                           N N  COCH.sub.3                   IA-122                                                                              N                                                                                 ##STR520##  H            H   CH.sub.3                                                                           N N  COCH.sub.3                   IA-123                                                                              N                                                                                 ##STR521##                                                                                 ##STR522##  H   OCH.sub.3                                                                          N N  COCH.sub.3                                                                            200                  IA-124                                                                              N                                                                                 ##STR523##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-125                                                                              N                                                                                 ##STR524##                                                                                 ##STR525##  H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-126                                                                              N                                                                                 ##STR526##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-127                                                                              N                                                                                 ##STR527##                                                                                 ##STR528##  H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-128                                                                              N                                                                                 ##STR529##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-129                                                                              N                                                                                 ##STR530##                                                                                 ##STR531##  H   OCH.sub.3                                                                          N N  COCH.sub.3                                                                            184                  IA-130                                                                              N                                                                                 ##STR532##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                                                                            225                  IA-131                                                                              N                                                                                 ##STR533##                                                                                 ##STR534##  H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-132                                                                              N                                                                                 ##STR535##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-133                                                                              N                                                                                 ##STR536##                                                                                 ##STR537##  H   OCH.sub.3                                                                          N N  COCH.sub.3                                                                            232                  IA-134                                                                              N                                                                                 ##STR538##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-135                                                                              N                                                                                 ##STR539##                                                                                 ##STR540##  H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-136                                                                              N                                                                                 ##STR541##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-137                                                                              N                                                                                 ##STR542##                                                                                 ##STR543##  H   OCH.sub.3                                                                          N N  COCH.sub.3                                                                            198                  IA-138                                                                              N                                                                                 ##STR544##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-139                                                                              N                                                                                 ##STR545##                                                                                 ##STR546##  H   OCH.sub.3                                                                          N N  COCH.sub.3                                                                            250                  IA-140                                                                              N                                                                                 ##STR547##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                                                                            205                  IA-141                                                                              N                                                                                 ##STR548##                                                                                 ##STR549##  H   OCHF.sub.2                                                                         N CH COCHF.sub.2                  IA-142                                                                              N                                                                                 ##STR550##                                                                                 ##STR551##  H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-143                                                                              N                                                                                 ##STR552##                                                                                 ##STR553##  H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-144                                                                              N                                                                                 ##STR554##                                                                                 ##STR555##  H   CH.sub.3                                                                           N N  CCH.sub.3                    IA-145                                                                              N                                                                                 ##STR556##  H            H   CH.sub.3                                                                           N N  CCH.sub.3                    IA-146                                                                              N                                                                                 ##STR557##                                                                                 ##STR558##  H   CH.sub.3                                                                           N N  CCH.sub.3                    IA-147                                                                              N                                                                                 ##STR559##                                                                                 ##STR560##  H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-148                                                                              N                                                                                 ##STR561##                                                                                 ##STR562##  H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-149                                                                              N                                                                                 ##STR563##                                                                                 ##STR564##  H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-150                                                                              N                                                                                 ##STR565##                                                                                 ##STR566##  H   OCH.sub.3                                                                          N N  CCl                          IA-151                                                                              N                                                                                 ##STR567##                                                                                 ##STR568##  H   C.sub.2 H.sub.5                                                                    N N  COCH.sub.3                   IA-152                                                                              N                                                                                 ##STR569##                                                                                 ##STR570##  H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-153                                                                              N                                                                                 ##STR571##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-154                                                                              N                                                                                 ##STR572##  H            H   OCH.sub.3                                                                          N N  CCH.sub.3                    IA-155                                                                              N                                                                                 ##STR573##                                                                                 ##STR574##  H   OCH.sub.3                                                                          N N  CNHC.sub.2 H.sub.5           IA-156                                                                              N                                                                                 ##STR575##                                                                                 ##STR576##  H   OC.sub.2 H.sub.5                                                                   N N  CNHCH.sub.3                  IA-157                                                                              N                                                                                 ##STR577##                                                                                 ##STR578##  H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-158                                                                              N                                                                                 ##STR579##                                                                                 ##STR580##  H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-159                                                                              N                                                                                 ##STR581##                                                                                 ##STR582##  H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-160                                                                              N                                                                                 ##STR583##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-161                                                                              N                                                                                 ##STR584##                                                                                 ##STR585##  H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-162                                                                              N                                                                                 ##STR586##  H            H   OCH.sub. 3                                                                         N CH COCH.sub.3                   IA-163                                                                              N                                                                                 ##STR587##                                                                                 ##STR588##  H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-164                                                                              N                                                                                 ##STR589##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-165                                                                              N                                                                                 ##STR590##                                                                                 ##STR591##  H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-166                                                                              N                                                                                 ##STR592##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-167                                                                              N                                                                                 ##STR593##                                                                                 ##STR594##  H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-168                                                                              N                                                                                 ##STR595##                                                                                 ##STR596##  H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             217                  IA-169                                                                              N                                                                                 ##STR597##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             252                  IA-170                                                                              N                                                                                 ##STR598##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-171                                                                              N                                                                                 ##STR599##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-172                                                                              N                                                                                 ##STR600##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-173                                                                              N                                                                                 ##STR601##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                   IA-174                                                                              N                                                                                 ##STR602##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-175                                                                              N                                                                                 ##STR603##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-176                                                                              N                                                                                 ##STR604##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-177                                                                              N                                                                                 ##STR605##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-178                                                                              N                                                                                 ##STR606##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IA-179                                                                              N                                                                                 ##STR607##  H            CH.sub.3                                                                          CH.sub.3                                                                           N CH CCH.sub.3                                                                             208                  IA-180                                                                              N                                                                                 ##STR608##  H            OCH.sub.3                                                                         CH.sub.3                                                                           N CH CCH.sub.3                    IA-181                                                                              N                                                                                 ##STR609##  H            SCH.sub.3                                                                         CH.sub.3                                                                           N CH CCH.sub.3                    IB-182                                                                              N                                                                                 ##STR610##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                    IB-183                                                                              N                                                                                 ##STR611##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                   IB-184                                                                              H                                                                                 ##STR612##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IB-185                                                                              N                                                                                 ##STR613##  H            H   CH.sub.3                                                                           N N  COCH.sub.3                   IB-186                                                                              N                                                                                 ##STR614##  H            H   CH.sub.3                                                                           N N  COCH.sub.3                   IB-187                                                                              N                                                                                 ##STR615##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IB-188                                                                              N                                                                                 ##STR616##  H            H   OCH.sub.3                                                                          N CH CCl                          IB-189                                                                              N                                                                                 ##STR617##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                   IB-190                                                                              N                                                                                 ##STR618##  H            H   OCH.sub.3                                                                          N N  COCH.sub.3                   IB-191                                                                              N                                                                                 ##STR619##  H            H   CH.sub.3                                                                           N N  COCH.sub.3                   IC-192                                                                              N                                                                                 ##STR620##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             206                  IA-193                                                                              N                                                                                 ##STR621##                                                                                 ##STR622##  H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     161                  IA-194                                                                              N                                                                                 ##STR623##                                                                                 ##STR624##  H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     204                  IA-195                                                                              N                                                                                 ##STR625##                                                                                 ##STR626##  H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     206                  IA-196                                                                              N                                                                                 ##STR627##  H            H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     190                  IA-197                                                                              N                                                                                 ##STR628##                                                                                 ##STR629##  H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     134                  IA-198                                                                              N                                                                                 ##STR630##                                                                                 ##STR631##  H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     160                  IA-199                                                                              N                                                                                 ##STR632##                                                                                 ##STR633##  H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     237                  IA-200                                                                              N                                                                                 ##STR634##                                                                                 ##STR635##  H   OCH.sub.3                                                                          N N  COC.sub.2 H.sub.5                                                                     200                  IA-201                                                                              N                                                                                 ##STR636##  H            H   OCH.sub.3                                                                          N N  COC.sub.2 H.sub.5                                                                     189                  IA-202                                                                              N                                                                                 ##STR637##                                                                                 ##STR638##  H   OCH.sub.3                                                                          N N  COC.sub.2 H.sub.5                                                                     183                  IA-203                                                                              N                                                                                 ##STR639##                                                                                 ##STR640##  H   OCH.sub.3                                                                          N N  COC.sub.2 H.sub.5                                                                     190                  IA-204                                                                              N                                                                                 ##STR641##  H            H   OCH.sub.3                                                                          N N  COC.sub.2 H.sub.5                                                                     152                  IB-205                                                                              N                                                                                 ##STR642##                                                                                 ##STR643##  CH.sub.3                                                                          H    N CH CH      155                  IB-206                                                                              N                                                                                 ##STR644##                                                                                 ##STR645##  CH.sub.3                                                                          CH.sub.3                                                                           N CH CCH.sub.3                                                                             195                  IB-207                                                                              N                                                                                 ##STR646##  H            CH.sub.3                                                                          H    N CH CH      185                  IB-208                                                                              N                                                                                 ##STR647##  H            CH.sub.3                                                                          CH.sub.3                                                                           N CH CCH.sub.3                                                                             202                  IA-209                                                                              CH                                                                                ##STR648##                                                                                 ##STR649##  H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             177                  IA-210                                                                              N                                                                                 ##STR650##                                                                                 ##STR651##  H   H    N CH CH      210                  IA-211                                                                              N                                                                                 ##STR652##  H            H   H    N CH CH      213                  IA-212                                                                              CH                                                                                ##STR653##                                                                                 ##STR654##  H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             340                  IA-213                                                                              CH                                                                                ##STR655##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             191                  IC-214                                                                              N                                                                                 ##STR656##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             217                  IA-215                                                                              N                                                                                 ##STR657##                                                                                 ##STR658##  H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             195                  IA-216                                                                              N                                                                                 ##STR659##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             240                  IA-217                                                                              N                                                                                 ##STR660##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             152                  IC-218                                                                              N                                                                                 ##STR661##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                                                                            213                  IC-219                                                                              N                                                                                 ##STR662##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                                                                            225                  IC-220                                                                              N                                                                                 ##STR663##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                                                                            210                  IC-221                                                                              N                                                                                 ##STR664##  H            CH.sub.3                                                                          OCH.sub.3                                                                          N CH COCH.sub.3                                                                            213                  IC-222                                                                              N                                                                                 ##STR665##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                                                                            215                  IA-223                                                                              N                                                                                 ##STR666##  H            H   CH.sub.3                                                                           N N  COCH.sub.3                                                                            212                  IC-224                                                                              N                                                                                 ##STR667##  H            H   CH.sub.3                                                                           N CH COCH.sub.3                                                                            139                  IA-225                                                                              N                                                                                 ##STR668##                                                                                 ##STR669##  H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5            IA-226                                                                              N                                                                                 ##STR670##                                                                                 ##STR671##  H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     144                  IA-227                                                                              N                                                                                 ##STR672##  H            H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     192                  IA-228                                                                              N                                                                                 ##STR673##                                                                                 ##STR674##  H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     227                  IA-229                                                                              N                                                                                 ##STR675##                                                                                 ##STR676##  H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     205                  IA-230                                                                              N                                                                                 ##STR677##                                                                                 ##STR678##  H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     234                  IA-231                                                                              N                                                                                 ##STR679##  H            H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.                     IA-232                                                   162                        N b.5                                                                             ##STR680##                                                                                 ##STR681##  H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     203                  IA-233                                                                              N                                                                                 ##STR682##                                                                                 ##STR683##  H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                      72                  IA-234                                                                              N                                                                                 ##STR684##                                                                                 ##STR685##  H   OCH.sub.3                                                                          N N  COCH.sub.3                                                                            228                  IA-235                                                                              N                                                                                 ##STR686##                                                                                 ##STR687##  H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     180                  IA-236                                                                              N                                                                                 ##STR688##                                                                                 ##STR689##  H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     170                  IA-237                                                                              N                                                                                 ##STR690##  H            H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     215                  IA-238                                                                              N                                                                                 ##STR691##                                                                                 ##STR692##  H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     188                  IA-239                                                                              N                                                                                 ##STR693##  H            H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     210                  IA-240                                                                              N                                                                                 ##STR694##                                                                                 ##STR695##  H   OCH.sub.3                                                                          N N  COCH.sub.3                                                                            219                  IA-241                                                                              CH                                                                                ##STR696##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             231                  IA-242                                                                              N                                                                                 ##STR697##  H            H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5                                                                     186                  IC-243                                                                              N                                                                                 ##STR698##  H            H   CH.sub.3                                                                           N CH COCH.sub.3                                                                            190                  IA-244                                                                              N                                                                                 ##STR699##  H            H   OCH.sub.3                                                                          N CH COCH.sub.3                                                                            275                  IA-245                                                                              N                                                                                 ##STR700##  H            H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5            IA-246                                                                              N                                                                                 ##STR701##  H            H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5            IA-247                                                                              N                                                                                 ##STR702##  H            H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5            IA-248                                                                              N                                                                                 ##STR703##                                                                                 ##STR704##  H   OCH.sub.3                                                                          N N  COC.sub.2 H.sub.5            IA-249                                                                              N                                                                                 ##STR705##                                                                                 ##STR706##  H   OCH.sub.3                                                                          N N  COC.sub.2 H.sub.5            IA-250                                                                              N                                                                                 ##STR707##  H            H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5            IA-251                                                                              N                                                                                 ##STR708##  H            H   OC.sub.2 H.sub.5                                                                   N N  COC.sub.2 H.sub.5            IA-252                                                                              N                                                                                 ##STR709##  H            H   CH.sub.3                                                                           N CH CCH.sub.3                                                                             192                  __________________________________________________________________________

The preparation of some more compounds according to the invention isdescribed below with reference to examples.

Preparation of the compound mentioned in Table 6 as Example (IC-224)##STR710## 3.0 g (0.025 mol) of dimethylformamide dimethyl acetal areadded to a solution of 9.3 g ((0.025 mol) ofN'-(4-methyl-6-methoxy-pyrimidin-2-yl)-N"-amino-N"'-(2-chlorophenylsulphonyl)-guanidinein 100 ml of methanol, and the reaction mixture is stirred for 2 hoursat 20° C. During this process, the product is obtained in the form ofcrystals and is isolated by filtering off with suction.

8.0 g (84% of theory) of4-(4-methyl-6-methoxypyrimidin-2-yl)-3-(2-chloro-phenylsulphonylamino)-triazoleof melting point 139° C. are obtained.

Preparation of the compound mentioned in Table 6 as Example (IA-223):##STR711## 2.7 g (0.023 mol) of dimethylformamide dimethyl acetal areadded to a solution of 6.3 g (0.015 mol) ofN'-(4-methyl-6-methoxy-s-triazin-2-yl-amino)-N'-(2-trifluoromethoxy-phenylsulphonyl)-guanidinein 20 ml of methanol, and the reaction mixture is refluxed to boilingpoint for 30 minutes. After cooling to room temperature (approximately20° C.), the product is isolated by filtering off with suction andrecrystallized from methanol.

4.5 g (70% of theory) of1-(4-methyl-6-methoxy-s-triazin-2-yl)-3-(2-trifluoromethoxy-phenylsulphonylamino)triazoleof melting point 212° C. are obtained.

Preparation of the compound listed in Table 6 as Example (IA-209):##STR712## 20.2 g (0.18 mol) of 1,4-diazabicyclo-[2,2,2]-octane (DABCO)are added to a stirred mixture which has been cooled to 0° C. of 5.73 g(0.03 mol) of 1-(4,6-dimethylpyrimidin-2-yl)-3-amino-2-pyrazoline, 31.3g (0.12 mol) of 2-methoxycarbonyl-benzenesulphonyl chloride and 200 mlof methylene chloride, and the reaction mixture is stirred for 18 hoursat 20° C. under atmospheric pressure, with contact to atmosphericoxygen. The reaction solution is then washed with water and is driedover sodium sulphate. The mixture is filtered and evaporated, and theresidue is crystallized using ethyl acetate. The crystalline product isisolated by filtering off with suction.

5.9 g (33% of theory) of1-(4,6-dimethylpyrimidin-2-yl)-3-(N,N-bis-(2-methoxycarbonyl-phenylsulphonyl)amino)-pyrazoleof melting point 177° C. are obtained.

Preparation of the compound mentioned in Table 6 as Example (IA-242):##STR713## 2.93 g (0.022 mol) of aluminum chloride are added at roomtemperature to a mixture of 5.02 g (0.02 mol) of1-(4,6-diethoxy-s-triazin-2-yl)-3-amino-triazole and 60 ml of pyridine.This results in an exothermic reaction, and the temperature rises toabove 40° C. After cooling to 10° C. to 20° C., 4.2 g (0.02 mol) of2-chloro-benzenesulphonyl chloride are added to the stirred mixture, andthe reaction mixture is then stirred for 4 hours at 50° C. After 12 morehours of stirring at 20° C., the mixture is stirred into 480 ml of 3Nhydrochloric acid, the mixture is stirred for 30 minutes, filtered offwith suction and washed with water. The crude product is recrystallizedfrom ethanol.

6.1 g (72% of theory) of1-(4,6-diethoxy-s-triazin-2-yl)-3-(2-chloro-phenylsulphonylamino)-triazoleof melting point 186° C. are obtained.

Preparation of the dimethylammonium salt of the compound mentioned inTable 6 as Example (IA-130): ##STR714## A mixture of 8.0 g (0.02 mol) ofN'-(4,6-dimethoxy-s-triazin-2-yl-amino)-N"-(2-chloro-phenylsulphonyl)-guanidine,4.5 g (0.0375 mol) of dimethylformamide dimethyl acetal and 30 ml ofmethanol is stirred for 10 minutes at 60° C. After stirring for one morehour at 20° C., the product obtained in the form of crystals is isolatedby filtering off with suction.

4.6 g (52% of theory) of the dimethylammonium salt of1-(4,6-dimethoxy-s-triazin-2-yl)-3-(2-chlorophenylsulphonylamino)-triazoleof melting point 145° C. are obtained.

STARTING SUBSTANCES OF THE FORMULA (II) EXAMPLE (II-1) ##STR715##

A mixture of 37.2 g (0.2 mol) of2-methylsulphonyl-4,6-dimethyl-pyrimidine, 33.6 g (0.4 mol) of3-amino-1,2,4-triazole, 27.6 g (0.2 mol) of potassium carbonate and 300ml of acetonitrile is boiled to reflux for 3 hours. The mixture is thenevaporated under a waterpump vacuum, the residue is stirred with 300 mlof water, a pH of 7 is adjusted with hydrochloric acid and thecrystalline product is isolated by filtering off with suction. Theresulting crude product is purified by chromatography over a silica gelcolumn using methylene chloride/methanol (vol. 9:1) as the eluant. Thesolvent is carefully stripped off under a waterpump vacuum of each ofthe two eluate fractions obtained.

As the first fraction, 10.2 g (27% of theory) of3-amino-1-(4,6-dimethyl-pyrimidin-2-yl)-1,2,4-triazole (IIA-1) ofmelting point 235° C.-238° C. are obtained

9.8 g (26% of theory) of5-amino-1-(4,6-dimethylpyrimidin-2-yl)-1,2,4-triazole (IIB-1) of meltingpoint 230° C.-232° C. are obtained as the second fraction.

EXAMPLE (II-2) ##STR716##

A mixture of 11.2 g (0.06 mol) of4,6-dimethyl-2-methylsulphonyl-pyrimidine, 5.9 g (0.06 mol) of3-amino-5-methyl-1,2,4-triazole, 8.3 g (0.06 mol) of potassium carbonateand 100 ml of acetonitrile is boiled to reflux for 5 hours. Afterevaporating, the residue is stirred into 100 ml of water, the product,which in this process is obtained in the form of crystals, is isolatedby filtering off with suction, washed with water and recrystallized fromacetonitrile.

4.6 g (37% of theory) of1-(4,6-dimethylpyrimidin-2-yl)-5-amino-3-methyl-1,2,4-triazole ofmelting point 237° C. are obtained.

EXAMPLE (II-3) ##STR717##

A mixture of 60 g (0.3 mol) of 4,6-diethoxy-2-hydrazino-s-triazine, 44 g(0.3 mol) of S,S-dimethyl cyanimino-dithiocarbonate and 300 ml ofethanol is boiled to reflux for 12 hours. After cooling to roomtemperature (approximately 20° C. ), the product which is obtained inthe form of crystals is isolated by filtering off with suction.

73.8 g (83% of theory) of1-(4,6-diethoxy-s-triazin-2-yl)-5-amino-3-methylthio-1,2,4-triazole ofmelting point 201° C. are obtained.

EXAMPLE (II-4) ##STR718##

A mixture of 22.4 g (0.09 mol) of(4,6-dimethoxypyrimidin-2-yl-amino)-guanidine hydrochloride, 12.6 g(0.11 mol) of dimethylformamide dimethyl acetal and 150 ml ofacetonitrile are boiled to reflux for 5 hours. After cooling to -10° C.,the product obtained in the form of crystals is isolated by filteringoff with suction.

10.9 g (54% of theory) of1-(4,6-dimethoxypyrimidin-2-yl)-3-amino-1,2,4-triazole of melting point219° C. are obtained.

The compounds of the formula (II), which is specified in more detail byformulae (IIA), (IIB) and (IIC), which are listed in Table 7 below canbe prepared in analogy to Examples (II-1) to (II-4): ##STR719## (InTable 7 below, A is indicated in each case instead of A').

                  TABLE 7                                                         ______________________________________                                        Examples of the compounds of the formula (II)                                 Ex-                                         Melting                           ample                                       Point                             No.   A     R.sup.3  R.sup.4                                                                             X   Y    Z       (°C.)                      ______________________________________                                        IIB-5 N     CH.sub.3 H     N   CH   CH      223                               IIA-6 N     CH.sub.3 CH.sub.3                                                                            N   CH   C--CH.sub.3                                                                           211                               IIB-7 N     SCH.sub.3                                                                              OCH.sub.3                                                                           N   CH   C--OCH.sub.3                                                                          204                               IIB-8 N     SCH.sub.3                                                                              CH.sub.3                                                                            N   CH   C--OCH.sub.3                                                                          220                               IIB-9 N     SCH.sub.3                                                                              OCH.sub.3                                                                           N   N    C--OC.sub.2 H.sub.5                                                                   188                               IIB-10                                                                              N     SCH.sub.3                                                                              OCH.sub.3                                                                           N   N    C--OCH.sub.3                                                                          198                               IIA-11                                                                              N     H        OCH.sub.3                                                                           N   N    C--OCH.sub.3                                                                          233                               IIA-12                                                                              N     H        OC.sub.2 H.sub.5                                                                    N   N    C--OC.sub.2 H.sub.5                                                                   226                               IIA-13                                                                              N     H        OCH.sub.3                                                                           N   N    C--OC.sub.2 H.sub.5                                                                   211                               IIA-14                                                                              N     H        H     N   H    C--H    206                               IIB-15                                                                              N     SCH.sub.3                                                                              H     N   CH   CH      235                               IIB-16                                                                              N     SO.sub.2 CH.sub.3                                                                      H     N   CH   CH      276                               IIA-17                                                                              N     H        CH.sub. 3                                                                           N   CH   C--OCH.sub.3                                                                          229                               ______________________________________                                    

STARTING SUBSTANCES of the FORMULAE (IVA) and (IVB) EXAMPLE (IV-1)##STR720##

1.3 g (0.025 mol) of hydrazine hydrate are added, initially at 20° C.,to a stirred suspension of 15.9 g (0.025 mol) ofN'-(4,6-dimethoxy-pyrimidin-2-yl)-N"-methoxy-N"-(2-methoxycarbonyl-phenylsulphonyl)-N"'-(2-methoxycarbonyl-benzylsulphonyl)-guanidinein 100 ml of methanol, during which process the temperature of thereaction mixture rises to 30° C. and a clear solution is formed. Theproduct which is separated in the form of crystals after four hours ofstirring at 20° C. to 30° C. is isolated by filtering off with suction.

9.5 g (89% of theory) ofN'-(4,6-dimethoxypyrimidin-2-yl)-N"-amino-N"'-(2-methoxycarbonyl-benzylsulphonyl)-guanidineof melting point 166° C. are obtained.

EXAMPLE (IV-2) ##STR721##

A solution of 3.8 g (0.01 mol) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-amino-N"'-(2-methoxycarbonyl-thien-3-yl-sulphonyl)-guanidinein 100 ml of ethanol is boiled to reflux for 15 hours. After thereaction mixture has been cooled to 0° C., the product separated out inthe form of crystals is isolated by filtering off with suction.

2.2 g (58% of theory) of N'-(4,6-dimethylpyrimidin-2-yl-amino)-N"-(2-methoxycarbonyl-thien-3-yl-sulphonyl)-guanidine ofmelting point 213° C. are obtained.

EXAMPLE (IV-3) ##STR722##

A mixture of 8.8 g (0.02 mol) ofN'-(4-methyl-6-methoxy-s-triazin-2-yl)-N"-(2-trifluoromethoxy-phenyl-sulphonyl)-S-methyl-isothiourea,1.0 g (0.02 mol of hydrazine hydrate and 100 ml of ethanol is stirredfor 60 minutes at 20° C. The product which during this process separatesout in the form of crystals is isolated by filtering off with suction.

6.4 g (76% of theory) of(N'-(4-methyl-6-methoxy-s-triazin-2-yl-amino)-N"-(2-trifluoromethoxyphenylsulphonyl)-guanidineof melting point 245° C. are obtained.

The compounds, of the formulae (IVA) and (IVB), which are listed inTable 8 below can be prepared in analogy to Example (IV-1) to (IV-3):##STR723##

                                      TABLE 8                                     __________________________________________________________________________    Examples of the compounds of the formula (IVA) and (IVB)                      Example No.                                                                          R.sup.1     R.sup.4                                                                           X Y  Z     Melting Point (°C.)                  __________________________________________________________________________    IVA-4                                                                                            OCH.sub.3                                                                         N CH COCH.sub.3                                                                          134                                         IVA-5                                                                                 ##STR724## OCH.sub.3                                                                         N CH COCH.sub.3                                                                          159                                         IVA-6                                                                                 ##STR725## CH.sub.3                                                                          N CH CCH.sub.3                                                                            98                                         IVA-7                                                                                 ##STR726## CH.sub.3                                                                          N N  COCH.sub.3                                                                          amorphous                                   IVA-8                                                                                 ##STR727## OCH.sub.3                                                                         N N  COCH.sub.3                                                                          amorphous                                   IVA-9                                                                                 ##STR728## CH.sub.3                                                                          N CH COCH.sub.3                                                                          166                                         IVA-10                                                                                ##STR729## CH.sub.3                                                                          N CH CCH.sub.3                                                                           105                                         IVA-11                                                                                ##STR730## CH.sub.3                                                                          N N  CCH.sub.3                                                                           102                                         IVB-12                                                                                ##STR731## OCH.sub.3                                                                         N N  COCH.sub.3                                                                          222                                         IVB-13                                                                                ##STR732## OCH.sub.3                                                                         N N  COCH.sub.3                                                                          138                                         IVB-14                                                                                ##STR733## CH.sub.3                                                                          N N  COCH.sub.3                                                                          230                                         IVB-15                                                                                ##STR734## CH.sub.3                                                                          N N  COCH.sub.3                                                                          208                                         IVB-16                                                                                ##STR735## CH.sub.3                                                                          N N  COCH.sub.3                                                                          195                                         IVB-17                                                                                ##STR736## CH.sub.3                                                                          N CH COCH.sub.3                                                                          262                                         IVB-18                                                                                ##STR737## OCH.sub.3                                                                         N CH COCH.sub.3                                                                          195                                         IVB-19                                                                                ##STR738## OCH.sub.3                                                                         N N  COCH.sub.3                                                                          215                                         IVB-20                                                                                ##STR739## CH.sub.3                                                                          N N  CSCH.sub.3                                                                          202                                         IVB-21                                                                                ##STR740## CH.sub.3                                                                          N N  COCH.sub.3                                                                          235                                         IVB-22                                                                                ##STR741## OCH.sub.3                                                                         N N  COCH.sub.3                                                                          199                                         __________________________________________________________________________

STARTING SUBSTANCES OF THE FORMULA (VI) EXAMPLE (VI-1) ##STR742##

A solution, prepared from 0.6 g (0.026 mol) of sodium and 30 ml ofethanol, and 5.3 g (0.1 mol) of acrylonitrile are added in succession toa mixture of 13.8 g (0.1 mol) of 4,6-dimethyl-2-hydrazino-pyrimidine, 27g (0.1 mol) of sodium methoxide and 80 ml of methanol. The reactionmixture is boiled to reflux for 18 hours and then evaporated. Theresidue is taken up in 200 ml of water, and this solution is brought toa pH of 6 using hydrochloric acid. 20 g of sodium chloride are thenadded, and the mixture is cooled to 10° C. The product which during thisprocess separates out in the form of crystals is isolated by filteringoff with suction.

10.8 g (57% of theory) of1-(4,6-dimethyl-pyrimidin-2-yl)-3-amino-pyrazoline of melting point 205°C. are obtained.

STARTING SUBSTANCES OF THE FORMULA (IX) EXAMPLE (IX-1) ##STR743##

A mixture of 32.7 g (0.15 mol) of4,6-dimethoxy-2-methylsulphonyl-pyrimidine, 7.3 g (0.15 mol) ofhydrazine hydrate, 21 g (0.15 mol) of triethylamine and 200 ml ofethanol is stirred for 24 hours at 25° C. After the addition of afurther 3.7 ml (0.076 mol) of hydrazine hydrate, the reaction mixture isstirred for a further 24 hours at 25° C. and then diluted with 200 ml ofpetroleum ether. The product which has been separated out in the form ofcrystals is isolated by filtering off with suction.

18.9 g (74% of theory) of 4,6-dimethoxy-2-hydrazino-pyrimidine ofmelting point 94° C. are obtained.

STARTING SUBSTANCES OF THE FORMULA (XIB) EXAMPLE (XI-1) ##STR744##

A mixture of 17.0 g (0.1 mol) of 4,6-dimethoxy-2-hydrazino-pyrimidine,8.3 ml of concentrated hydrochloric acid, 4.2 g (0.1 mol) of cyanamideand 100 ml of ethanol is boiled to reflux for 18 hours. The mixture isthen evaporated, the residue is crystallized using diethyl ether, andthe crystalline product is isolated by filtering off with suction.

22.9 g (92% of theory) of (4,6-dimethoxy-pyrimidin-2-yl-amino)-guanidinehydrochloride of melting point 214° C. are obtained.

The compounds, of the formula (XIB), which are listed in Table 9 belowcan be prepared in analogy to Example (XI-1): ##STR745##

                  TABLE 9                                                         ______________________________________                                        Examples of the compounds of the formula (XIB)                                Example                                Melting                                No.     R.sup.4  X      Y     Z        Point (°C.)                     ______________________________________                                        XIB-2   CH.sub.3 N      CH    C--CH.sub.3                                                                            218                                    XIB-3   OCH.sub.3                                                                              N      CH    C--Cl    237                                    XIB-4   OC.sub.2 H.sub.5                                                                       N      N     C--OC.sub.2 H.sub.5                                                                    169                                    XIB-5   OCH.sub.3                                                                              N      N     C--OCH.sub.3                                                                           235                                    XIB-6   OCH.sub.3                                                                              N      N     C--OC.sub.2 H.sub.5                                                                    220                                    ______________________________________                                    

USE EXAMPLES EXAMPLE A Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours,watered with the preparation of the active compound. It is expedient tokeep constant the amount of water per unit area. The concentration ofthe active compound in the preparation is of no importance, only theamount of active compound applied per unit area being decisive. Afterthree weeks, the degree of damage to the plants is rated in % damage incomparison to the development of the untreated control. The figuresdenote:

0%=no action (like untreated control)

100%=total destruction.

In this test, for example, the compounds according to PreparationExamples (IA-2), (IA-3), (IA-6), (IA-8) and (IA-223) show a clearlysuperior activity compared with the prior art. This applies inparticular also to the compounds according to Preparation Examples(IA-25) and (IA-68).

EXAMPLE B Post-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with thepreparation of the active compound in such a way as to apply theparticular amounts of active compound desired per unit area. Theconcentration of the spray liquor is so chosen that the particularamounts of active compound desired are applied in 2,000 l of water/ha.After three weeks, the degree of damage to the plants is rated in %damage in comparison to the development of the untreated control. Thefigures denote:

0%=no action (like untreated control)

100%=total destruction.

In this test, for example, the compounds according to PreparationExamples (IA-1), (IA-2), (IA-5), (IA-6), (IA-8), (IA-52) and (IA-3) showa clearly superior activity compared with the prior art. This alsoapplies to the compounds according to the Preparation Examples (IA-25)and (IA-68).

It will be appreciated that the instant specification and claims are setforth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:
 1. A compound of the formula ##STR746## in which R¹stands for the radical ##STR747## wherein R⁷ and R⁸ are identical ordifferent and stand for hydrogen, fluorine, chlorine, bromine, iodine,cyano, nitro, C₁ -C₆ -alkyl (which is optionally substituted byfluorine, chlorine, bromine, cyano, carboxyl, C₁ -C₄ -alkoxycarbonyl, C₁-C₄ -alkylamino-carbonyl, di-(C₁ -C₄ -alkyl)aminocarbonyl, hydroxyl, C₁-C₄ -alkoxy, formyloxy, C₁ -C₄ -alkyl-carbonyloxy, C₁ -C₄-alkoxycarbonyloxy, C₁ -C₄ -alkylamino-carbonyloxy, C₁ -C₄ -alkylthio,C₁ -C₄ -alkylsulphinyl, C₁ -C₄ -alkylsulphonyl, di-(C₁ -C₄-alkyl)-aminosulphonyl, C₃ -C₆ -cycloalkyl or phenyl), for C₂ -C₆-alkenyl (which is optionally substituted by fluorine, chlorine,bromine, cyano, C₁ -C₄ -alkoxy-carbonyl, carboxyl or phenyl), for C₂ -C₆-alkinyl (which is optionally substituted by fluorine, chlorine,bromine, cyano, C₁ -C₄ -alkoxycarbonyl, carboxyl or phenyl), for C₁ -C₄-alkoxy (which is optionally substituted by fluorine, chlorine, bromine,cyano, carboxyl, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkoxy, C₁ -C₄-alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl), for C₁-C₄ -alkylthio (which is optionally substituted by fluorine, chlorine,bromine, cyano, carboxyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄ -alkylthio, C₁-C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl), for C₃ -C₆ -alkenyloxy(which is optionally substituted by fluorine, chlorine, bromine, cyanoor C₁ -C₄ -alkoxycarbonyl), for C₂ -C₆ -alkenylthio (which is optionallysubstituted by fluorine, chlorine, bromine, cyano, nitro, C₁ -C₃-alkylthio or C₁ -C₄ -alkoxycarbonyl), C₃ -C₆ -alkinyloxy, C₃ -C₆-alkinylthio or for the radical --S(O)_(p--) --R⁹, p standing for thenumbers 1 or 2 andR⁹ standing for C₁ -C₄ -alkyl (which is optionallysubstituted by fluorine, chlorine, bromine, cyano or C₁ -C₄-alkoxy-carbonyl), C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyl, C₁ -C₄ -alkoxy, C₁-C₄ -alkoxy-C₁ -C₄ -alkylamino, C₁ -C₄ -alkylamino, di-(C₁ -C₄-alkyl)-amino or for the radical --NHOR¹⁰, R¹⁰ standing for C₁ -C₆-alkyl (which is optionally substituted by fluorine, chlorine, cyano, C₁-C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl, C₁ -C₄-alkylsulphonyl, C₁ -C₄ -alkyl-carbonyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄-alkylamino-carbonyl or di-(C₁ -C₄ -alkyl)-aminocarbonyl), for C₃ -C₆-alkenyl (which is optionally substituted by fluorine, chlorine orbromine), C₃ -C₆ -alkinyl, C₃ -C₆ -cycloalkyl, C₃ -C₆ -cycloalkyl-C₁ -C₂-alkyl, phenyl-C₁ -C₂ -alkyl (which is optionally substituted byfluorine, chlorine, nitro, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁-C₄ -alkoxy-carbonyl), for benzhydryl or for phenyl (which is optionallysubstituted by fluorine, chlorine, nitro, cyano, C₁ -C₄ -alkyl,trifluoromethyl, C₁ -C₄ -alkoxy, C₁ -C₂ -fluoroalkoxy, C₁ -C₄-alkylthio, trifluoromethylthio or C₁ -C₄ -alkoxy-carbonyl), R⁷ and R⁸furthermore stand for phenyl or phenoxy, for C₁ -C₄ -alkylcarbonylamino,C₁ -C₄ -alkoxycarbonylamino, C₁ -C.sub. 4 -alkylamino-carbonylamino,di-(C₁ -C₄ -alkyl)-amino-carbonylamino, or for the radical --CO--R¹¹,R¹¹ standing for C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy, C₃ -C₆ -cycloalkoxy, C₃-C₆ -alkenyloxy, C₁ -C₄ -alkylthio, amino, C₁ -C₄ -alkylamino, C₁ -C₄-alkoxyamino, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl-amino or di-(C₁ -C₄-alkyl)-amino (which are optionally substituted by fluorine and/orchlorine), R⁷ and R⁸ furthermore stand for C₁ -C₄ -alkylsulphonyloxy,di-(C₁ -C₄ -alkyl)-aminosulphonylamino or for the radical --CH═N--R¹²,R¹² standing for C₁ -C₆ -alkyl which is optionally substituted byfluorine, chlorine, cyano, carboxyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio,C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl, for benzyl which isoptionally substituted by fluorine or chlorine, for C₃ -C₆ -alkenyl orC₃ -C₆ -alkinyl, each of which is optionally-substituted by fluorine orchlorine, for phenyl which is optionally substituted by fluorine,chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, trifluoromethyl,trifluoromethoxy or trifluoromethylthio, for C₁ -C₆ -alkoxy, C₃ -C₆-alkenoxy, C₃ -C₆ -alkinoxy or benzyloxy, each of which is optionallysubstituted by fluorine and/or chlorine, for amino, C₁ -C₄ -alkylamino,chlorine, for amino, C₁ -C₄ -alkylamino, di-(C₁ -C₄ -alkyl)-amino,phenylamino, C₁ -C₄ -alkyl-carbonylamino, C₁ -C₄ -alkoxy-carbonyl-amino,phenylsulphonylamino which is optionally substituted by fluorine,chlorine, bromine or methyl,wherein furthermore R¹ stands for theradical ##STR748## wherein R¹³ stands for hydrogen or C₁ -C₄ -alkyl, R¹⁴and R¹⁵ are identical or different and stand for hydrogen, fluorine,chlorine, bromine, nitro, cyano, C₁ -C₄ -alkyl (which is optionallysubstituted by fluorine and/or chlorine), C₁ -C₄ -alkoxy (which isoptionally substituted by fluorine and/or chlorine), carboxyl, C₁ -C₄-alkoxy-carbonyl, C₁ -C₄ -alkylsulphonyl or di-(C₁ -C₄-alkyl)aminosulphonyl;wherein furthermore R¹ stands for the radical##STR749## wherein R¹⁶ and R¹⁷ are identical or different and stand forhydrogen, fluorine, chlorine, bromine, nitro, cyano, C₁ -C₄ -alkyl(which is optionally substituted by fluorine and/or chlorine) or C₁ -C₄-alkoxy (which is optionally substituted by fluorine and/orchlorine);wherein furthermore R¹ stands for the radical ##STR750##wherein R¹⁸ and R¹⁹ are identical or different and stand for hydrogen,fluorine, chlorine, bromine, nitro, cyano, C₁ -C₄ -alkyl (which isoptionally substituted by fluorine and/or chlorine), C₂ -C₄ -alkenyl(which is optionally substituted by fluorine and/or chlorine), C₁ -C₄-alkoxy (which is optionally substituted by fluorine and/or chlorine),for C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl(which are optionally substituted by fluorine and/or chlorine), and fordi-(C₁ -C₄ -alkyl)aminosulphonyl, C₁ -C₄ -alkoxy-carbonyl,dimethylaminocarbonyl or dioxolanyl;wherein furthermore R¹ stands forthe radical ##STR751## wherein R²⁰ and R²¹ are identical or differentand stand for hydrogen, fluorine, chlorine, bromine, C₁ -C₄ -alkyl(which is optionally substituted by fluorine and/or bromine), C₁ -C₄-alkoxy (which is optionally substituted by fluorine and/or chlorine),for C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl(which are optionally substituted by fluorine and/or chlorine), or fordi-(C₁ -C₄ -alkyl)-aminosulphonyl;wherein furthermore R¹ stands for theradical ##STR752## wherein R²² and R²³ are identical or different andstand for hydrogen, fluorine, chlorine, bromine, cyano, nitro, C₁ -C₄-alkyl (which is optionally substituted by fluorine, chlorine, C₁ -C₄-alkoxy and/or C₁ -C₄ -halogenoalkoxy), C₁ -C₄ -alkoxy (which isoptionally substituted by fluorine and/or chlorine), C₁ -C₄ -alkylthio,C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl (which is optionallysubstituted by fluorine and/or chlorine), di-(C₁ -C₄-alkyl)-amino-sulphonyl or C₁ -C₄ -alkoxycarbonyl, andA¹ stands foroxygen, sulphur or the grouping N--Z¹, Z¹ standing for hydrogen, C₁ -C₄-alkyl (which is optionally substituted by fluorine, chlorine, bromineor cyano), C₃ -C₆ -cycloalkyl, benzyl, phenyl (which is optionallysubstituted by fluorine, chlorine, bromine or nitro), C₁ -C₄-alkylcarbonyl, C₁ -C₄ -alkoxy-carbonyl or di-(C₁ -C₄-alkyl)-aminocarbonyl;wherein furthermore R¹ stands for the radical##STR753## wherein R²⁴ and R²⁵ are identical or different and stand forhydrogen, C₁ -C₄ -alkyl, halogen, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkoxyor C₁ -C₄ halogenoalkoxy,Y¹ stands for sulphur or the grouping N-R²⁶,R²⁶ standing for hydrogen or C₁ -C₄ -alkyl;wherein furthermore R¹ standsfor the radical ##STR754## wherein R²⁷ stands for hydrogen, C₁ -C₄-alkyl, phenyl or (iso)quinolinyl,R²⁸ stands for hydrogen, halogen,cyano, nitro, C₁ -C₄ -alkyl (which is optionally substituted by fluorineand/or chlorine), C₁ -C₄ -alkoxy (which is optionally substituted byfluorine and/or chlorine), dioxolanyl or C₁ -C₄ -alkoxy-carbonyl and R²⁹stands for hydrogen, halogen or C₁ -C₄ -alkyl;wherein furthermore R¹stands for the radical ##STR755## wherein R³⁰ stands for hydrogen,halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy-carbonyl;wherein furthermore R¹stands for the radical ##STR756## wherein R³¹ stands for C₁ -C₄ -alkylandR³² stands for C₁ -C₄ -alkyl,wherein furthermore R¹ stands for theradical ##STR757## wherein R³³ stands for hydrogen or methyl;R⁴ standsfor hydrogen, fluorine, chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄-halogenoalkyl, C₁ -C₂ -alkoxy-C₁ -C₂ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄-halogenoalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -halogenoalkylthio, amino, C₁-C₄ -alkylamino, dimethylamino or diethylamino, R⁶ stands for hydrogen,fluorine, chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -halogenoalkyl, C₁-C₄ -alkoxy, C₁ -C₄ -halogenoalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-alkyl-amino, dimethylamino or diethylamino.